Spirosilane-derived phosphine-phosphine oxide compound as well as preparation method and application thereof

Abstract

The invention discloses a spirosilane-derived phosphine-phosphine oxide compound as well as a preparation method and application thereof. The invention specifically discloses a spirosilane-derived phosphine-phosphine oxide compound as shown in a formula I or a formula II, which can be used for catalyzing an asymmetric Heck reaction and an asymmetric Sonogashira reaction, and has one or more of the following advantages: the catalytic activity is high; the enantioselectivity of the product is high.

Description

Technical Field

[0001] This invention relates to a spirosilane-derived phosphine-phosphine oxide compound, its preparation method, and its application. Background Technology

[0002] In transition metal-catalyzed asymmetric reactions, high reactivity and selectivity can be achieved through the use of chiral ligands. Since the synthesis of the first chiral phosphine ligand in 1968, various types of chiral phosphine ligands have been designed and synthesized. However, despite years of research and development, chiral phosphine-phosphine oxide ligands still face limitations, such as restrictions on the types of ligand-catalyzed reactions and a limited number of skeletal types. Therefore, designing and developing a novel chiral phosphine-phosphine oxide ligand is crucial to expanding the possibilities for transition metal-catalyzed asymmetric reactions. Summary of the Invention

[0003] The technical problem this invention aims to solve is the limited structural diversity and skeletal variety of chiral phosphine-phosphoxy ligands. Therefore, this invention discloses a spirosilane-derived phosphine-phosphoxy compound, its preparation method, and its applications. This type of compound can form metal complexes or mixtures with group III to thirteenth metal salts for catalyzing asymmetric organic synthesis reactions. It exhibits high enantioselectivity of the products and enhances catalytic activity. Particularly in palladium-catalyzed asymmetric Heck and Sonogashira reactions, it demonstrates excellent enantioselectivity and catalytic activity.

[0004] The present invention solves the above-mentioned technical problems through the following technical solutions.

[0005] This invention provides a compound as shown in Formula I or Formula II.

[0006] ;

[0007] Where n1, n2, n3 and n4 are independently 0, 1, 2 or 3;

[0008] R 1 R 1’ R 6 and R 6’ Independently H, halogen, -N(R) 1a (R) 1b ), R 1c -L 1 -、C6-C 14 aryl, with one or more R 1g Replacement C6-C 14 aryl, 5-6 membered heteroaryl, or with one or more R 1h Substituted 5-6 heteroaryl; the 5-6 heteroaryl and one or more R 1hIn the substituted 5-6-membered heteroaryl group, the number of heteroatoms in the heteroaryl group is independently 1-4, and the heteroatoms are selected from one or more of N, O and S;

[0009] Alternatively, when n1, n2, n3, and n4 are independently 2 or 3, two adjacent R 1 and the C atom connected to it, and / or, the two adjacent R atoms 1’ and the C atom connected to it, and / or, the two adjacent R atoms 6 and the C atom connected to it, and / or, the two adjacent R atoms 6’ Together with the C atom attached thereto, it independently forms a C3-C7 cycloalkyl, a 5-6 membered heterocycloalkyl, or a phenyl; wherein the number of heteroatoms in the 5-6 membered heterocycloalkyl is independently 1-3, and the heteroatoms are selected from one or more of N, O, and S;

[0010] R 1a and R 1b Independently H, C1-C8 alkyl, or C1-C8 alkyl-C(=O)-;

[0011] R 1c Independently H, C1-C8 alkyl, or C1-C8 alkyl substituted with one or more halogens. , benzyl or benzyl or benzyl with one or more R 1i Substituted benzyl;

[0012] L 1 Independently, it can be a linker, -O-, -C(=O)-, or -OC(=O)-;

[0013] R 1d R 1e and R 1f It is independently a C1-C8 alkyl, C1-C8 alkyl-O-, phenyl, or is substituted by one or more R 1i Substituted phenyl;

[0014] R 1g R 1h and R 1i Independently, it is a halogen, a C1-C8 alkyl group, a C1-C8 alkyl group substituted with one or more halogens, a C1-C8 alkyl-O-, a C1-C8 alkyl-C(=O)-, a C1-C8 alkyl-OC(=O)-, a C1-C8 alkyl-C(=O)-O-, a -NH2, a (C1-C8 alkyl-C(=O)-)NH-, a (C1-C8 alkyl-C(=O)-)2N-, or a C6-C 14 Aryl;

[0015] R 2 R 2’ R 3 R3’ R 7 R 7’ R 8 R 8’ R 9 and R 9’ Independently H, halogen, -N(R) 2a (R) 2b ), R 2c -L 2 -、C6-C 14 aryl, with one or more R 2g Replacement C6-C 14 aryl, 5-6 membered heteroaryl, or with one or more R 2h Substituted 5-6 heteroaryl; the 5-6 heteroaryl and one or more R 2h In the substituted 5-6 membered heteroaryl groups, the number of heteroatoms is independently 1-4, and the heteroatoms are selected from one or more of N, O and S;

[0016] R 2a and R 2b Independently H, C1-C8 alkyl, or C1-C8 alkyl-C(=O)-;

[0017] L 2 For connection keys, -O-, -C(=O)-, or -OC(=O)-;

[0018] R 2c It is independently a C1-C8 alkyl or a C1-C8 alkyl substituted with one or more halogens;

[0019] R 2g and R 2h Independently, it is a halogen, a C1-C8 alkyl group, a C1-C8 alkyl group substituted with one or more halogens, a C1-C8 alkyl-O-, a C1-C8 alkyl-C(=O)-, a C1-C8 alkyl-OC(=O)-, a C1-C8 alkyl-C(=O)-O-, a -NH2, a (C1-C8 alkyl-C(=O)-)NH-, or a (C1-C8 alkyl-C(=O)-)2N-;

[0020] Or, R 2 and R 3 Connected, R 2’ and R 3’ Connected, R 7 and R 8 Connected, R 8 and R 9 Connected, R 7’ and R 8’ Connected, and / or R 8’ and R 9’They are connected together with their C and C bonds to form C3-C7 cycloalkyl or phenyl groups;

[0021] R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently, H, C1-C8 alkyl, C1-C8 alkyl substituted with one or more halogens, C1-C8 alkyl (C=O)-, C1-C8 alkyl (C=O)NH-, [C1-C8 alkyl (C=O)]2N-, nitro, cyano, 3-7 membered cycloalkyl, C6-C 15 aryl, 5-14 heteroaryl, or with one or more R 4d Replacement C6-C 15 Aryl; in the 5-14 membered heteroaryl groups, the number of heteroatoms is independently 1-4, and the heteroatoms are selected from one or more of N, O and S;

[0022] R 4d Independently halogen, C1-C8 alkyl, C1-C8 alkyl-O-, C6-C 15 Aryl, -N(R) 4e (R) 4f ), nitro, cyano, or with one or more R 4i Replacement C6-C 15 aryl; wherein the C1-C8 alkyl and C1-C8 alkyl-O-, the C1-C8 alkyl is optionally surrounded by one or more elements selected from halogens or C6-C 14 Substitution of aryl groups;

[0023] R 4e and R 4f Independently H or C1-C8 alkyl;

[0024] R 4i Independently, it is a halogen, a C1-C8 alkyl group, a C1-C8 alkyl group substituted with one or more halogens, a C1-C8 alkyl-O-, a C1-C8 alkyl-C(=O)-, a C1-C8 alkyl-OC(=O)-, a C1-C8 alkyl-C(=O)-O-, a -NH2, a (C1-C8 alkyl-C(=O)-)NH-, or a (C1-C8 alkyl-C(=O)-)2N-;

[0025] Or, R 4 and R 5 Connected, R 4’ and R 5’ Connected, R 10 and R 11Connected, and / or R 10’ and R 11’ They are connected together with their C and C bonds to form C3-C7 cycloalkyl or phenyl groups;

[0026] This indicates a chiral silicon center, which is either S-configuration silicon or R-configuration silicon.

[0027] In some schemes, R 1 and R 1’ same.

[0028] In some schemes, R 2 and R 2’ same.

[0029] In some schemes, R 3 and R 3’ same.

[0030] In some schemes, R 4 and R 5 same.

[0031] In some schemes, R 4’ and R 5’ same.

[0032] In some schemes, R 6 and R 6’ same.

[0033] In some schemes, R 7 and R 7’ same.

[0034] In some schemes, R 8 and R 8’ same.

[0035] In some schemes, R 9 and R 9’ same.

[0036] In some schemes, R 10 and R 11 same.

[0037] In some schemes, R 10’ and R 11’ same.

[0038] In some schemes, R 1 R 1’ R 6 and R 6’ For H.

[0039] In some schemes, R 2 and R 2’ For H.

[0040] In some schemes, R 3 and R 3’ For H.

[0041] In some schemes, R 7 and R 7’ For H.

[0042] In some schemes, R 8 and R 8’ For H.

[0043] In some schemes, R 9 and R 9’ For H.

[0044] In some schemes, R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently C1-C8 alkyl, 3-7 membered cycloalkyl, C6-C 15 aryl, 5-14 heteroaryl, or with one or more R 4d Replacement C6-C 15 Aryl; in the 5-14 membered heteroaryl groups, the number of heteroatoms is independently 1-4, and the heteroatoms are selected from one or more of N, O and S.

[0045] In some schemes, R 4d Independently halogen, C1-C8 alkyl, C1-C8 alkyl-O-, C6-C 15 Aryl, -N(R) 4e (R) 4f ); wherein the C1-C8 alkyl group and the C1-C8 alkyl-O- group are optionally surrounded by one or more elements selected from halogens or C6-C 14 Substituents of aryl groups.

[0046] In some schemes, R 4e and R 4f It is independently a C1-C8 alkyl group.

[0047] In some schemes, R 4e and R 4f same.

[0048] In some schemes, when L 1 and L 2 When independently -OC(=O)-, the -OC(=O)- is -OC(=O)-. # ,# Indicates with R 1c Or R 2c The connected end.

[0049] In some schemes, when R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ When independently a C1-C8 alkyl group, the C1-C8 alkyl group is methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl, preferably isopropyl or tert-butyl.

[0050] In some schemes, when R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ When independently a 3-7 membered cycloalkyl group, the 3-7 membered cycloalkyl group is a 4-6 membered cycloalkyl group, preferably cyclobutyl, cyclopentyl or cyclohexyl, more preferably cyclohexyl.

[0051] In some schemes, when R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for C6-C 15 In the aryl case, the C6-C 15 The aryl group is C6-C. 10 Aryl, preferably phenyl or naphthyl.

[0052] In some schemes, when R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ When independently a 5-14 membered heteroaryl group, the 5-14 membered heteroaryl group is preferably a 5-10 membered heteroaryl group. , , or .

[0053] In some schemes, when R 4R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for one or more R 4d Replacement C6-C 15 In the aryl case, the C6-C 15 The aryl group is C6-C. 10 Aryl, preferably phenyl or naphthyl.

[0054] In some schemes, when R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for one or more R 4d Replacement C6-C 15 When aryl is used, the number of one or more is 1 to 7, preferably 1, 2 or 3.

[0055] In some schemes, when R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for one or more R 4d Replacement C6-C 15 Aryl, R 4d When the halogen is halogen, the halogen is F, Cl or Br, preferably F or Cl.

[0056] In some schemes, when R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for one or more R 4d Replacement C6-C 15 Aryl, R 4d When the alkyl group is C1-C8, the C1-C8 alkyl group is methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl, preferably methyl, isopropyl or tert-butyl.

[0057] In some schemes, when R 4R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for one or more R 4d Replacement C6-C 15 Aryl, R 4d When the C1-C8 alkyl-O- is methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl, preferably methyl or isopropyl.

[0058] In some schemes, when R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for one or more R 4d Replacement C6-C 15 Aryl, R 4d For C6-C 15 In the aryl case, the C6-C 15 The aryl group is C6-C. 10 Aryl, preferably phenyl.

[0059] In some schemes, when R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for one or more R 4d Replacement C6-C 15 Aryl, R 4d The alkyl group is C1-C8, and when the C1-C8 alkyl group is substituted by one or more halogens, the halogens are F, Cl or Br, preferably F.

[0060] In some schemes, when R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for one or more R 4d Replacement C6-C 15 Aryl, R 4dThe alkyl group is C1-C8, and when the C1-C8 alkyl group is replaced by one or more halogens, the one or more halogens are preferably three.

[0061] In some schemes, when R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for one or more R 4d Replacement C6-C 15 Aryl, R 4d It is a C1-C8 alkyl group, wherein the C1-C8 alkyl group is formed by one or more C6-C atoms. 14 When aryl is substituted, the C6-C 14 The aryl group is C6-C. 10 Aryl, preferably phenyl.

[0062] In some schemes, when R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for one or more R 4d Replacement C6-C 15 Aryl, R 4d It is a C1-C8 alkyl group, wherein the C1-C8 alkyl group is formed by one or more C6-C atoms. 14 When aryl substitution occurs, the C1-C8 alkyl group is methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl, preferably methyl.

[0063] In some schemes, when R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for one or more R 4d Replacement C6-C 15 Aryl, R 4d It is a C1-C8 alkyl group, wherein the C1-C8 alkyl group is formed by one or more C6-C atoms. 14 When aryl substitution occurs, one or more of the above is preferred.

[0064] In some schemes, when R 4 R4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for one or more R 4d Replacement C6-C 15 Aryl, R 4d It is a C1-C8 alkyl-O-, and when the C1-C8 alkyl is replaced by one or more halogens, the halogens are F, Cl or Br, preferably F.

[0065] In some schemes, when R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for one or more R 4d Replacement C6-C 15 Aryl, R 4d It is a C1-C8 alkyl-O-, wherein the C1-C8 alkyl group is replaced by one or more halogens, preferably three.

[0066] In some schemes, when R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for one or more R 4d Replacement C6-C 15 Aryl, R 4d The C1-C8 alkyl-O- is a C1-C8 alkyl group. When the C1-C8 alkyl group is substituted with one or more halogens, the C1-C8 alkyl group is methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl, preferably methyl.

[0067] In some schemes, when R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for one or more R 4d Replacement C6-C 15 Aryl, R 4dIt is a C1-C8 alkyl-O-, wherein the C1-C8 alkyl group is formed by one or more C6-C... 14 When aryl is substituted, the C6-C 14 The aryl group is C6-C. 10 Aryl, preferably phenyl.

[0068] In some schemes, when R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for one or more R 4d Replacement C6-C 15 Aryl, R 4d It is a C1-C8 alkyl-O-, wherein the C1-C8 alkyl group is formed by one or more C6-C... 14 When aryl substitution occurs, one or more of the above is preferred.

[0069] In some schemes, when R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for one or more R 4d Replacement C6-C 15 Aryl, R 4d It is a C1-C8 alkyl-O-, wherein the C1-C8 alkyl group is formed by one or more C6-C... 14 When aryl substitution occurs, the C1-C8 alkyl group is methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl, preferably methyl.

[0070] In some schemes, when R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for one or more R 4d Replacement C6-C 15 Aryl, R 4d -N(R) 4e (R) 4f ), R 4e and R 4fWhen independently a C1-C8 alkyl group, the C1-C8 alkyl group is methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl, preferably methyl.

[0071] In some schemes, R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently C1-C8 alkyl, 3-7 membered cycloalkyl, C6-C 15 aryl, 5-14 heteroaryl, or with one or more R 4d Replacement C6-C 15 Aryl; in the 5-14 membered heteroaryl groups, the number of heteroatoms is independently 1-4, and the heteroatoms are selected from one or more of N, O and S.

[0072] In some schemes, R 4 and R 5 Independently for C6-C 15 aryl, 5-14 heteroaryl, or with one or more R 4d-1 Replacement C6-C 15 Aryl; in the 5-14 membered heteroaryl groups, the number of heteroatoms is independently 1-4, and the heteroatoms are selected from one or more of N, O and S;

[0073] R 4d-1 It is a C1-C8 alkyl or a C1-C8 alkyl-O-.

[0074] In some schemes, R 4’ and R 5’ Independently C1-C8 alkyl, 3-7 membered cycloalkyl, C6-C 15 aryl, 5-14 heteroaryl, or with one or more R 4d Replacement C6-C 15 Aryl; in the 5-14 membered heteroaryl groups, the number of heteroatoms is independently 1-4, and the heteroatoms are selected from one or more of N, O and S.

[0075] In some schemes, R 10 R 10’ R 11 and R 11’ Independently 3-7 membered cycloalkyl, C6-C 15 aryl or aryl with one or more R 4d-3 Replacement C6-C 15 Aryl;

[0076] R 4d-3It is a C1-C8 alkyl or a C1-C8 alkyl-O-; the C1-C8 alkyl is optionally coated with one or more halogens or C6-C 14 Substituents of aryl groups.

[0077] In some schemes, R 4 R 4 '、R 5 and R 5 Independently for Cy, t Bu、 i Pr, Ph, , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , or .

[0078] In some schemes, R 10 R 10’ R 11 and R 11’ Independently for Cy, t Bu, Ph, , , , , or .

[0079] In some embodiments, the compound represented by Formula I is a compound represented by Formula Ia or Formula Ib; the compound represented by Formula II is a compound represented by Formula IIa or Formula IIb.

[0080] ;

[0081] Where, n1, n2, n3, n4, R 1 R 1 '、R 2 R 2 '、R 3 R 3’ R 4 R 4 '、R 5 R 5 '、R 6 R 6’ R 7 R 7 '、R 8 R 8 '、R 9 R 9’ R 10 R 10’ R 11 and R 11’ The definition is the same as described in any of the previous schemes.

[0082] Those skilled in the art will understand that when the compound shown in Formula I is a compound shown in Formula Ia or Formula Ib, and the compound shown in Formula II is a compound shown in Formula IIa or Formula IIb, all of the compounds shown in Formula Ia, Formula Ib, Formula IIa, and Formula IIb are in a single configuration or exist with that configuration as the dominant configuration.

[0083] In some embodiments, the compound represented by Formula I is a compound represented by Formula Ic or Formula Id; the compound represented by Formula II is a compound represented by Formula IIc or Formula IId.

[0084] ;

[0085] Among them, R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ The definition is as described in the previous scheme.

[0086] In certain preferred embodiments of the present invention, the compound represented by Formula I or Formula II may have any of the following structures.

[0087] .

[0088] In some preferred embodiments of the present invention, the compound shown in Formula I is any one of the compounds shown in Formulas I-1 to I-210.

[0089] In some preferred embodiments of the present invention, the compound shown in Formula II is any one of the compounds shown in Formulas I-211 to I-228.

[0090] The present invention provides a catalyst composition comprising a metal complex formed by the compound of Formula I or II and a salt of a Group 3 to 13 metal and / or a mixture (in situ mixture) of the compound of Formula I or II and a Group 3 to 13 metal reagent.

[0091] The group 3 to 13 metals mentioned therein can be conventional group 3 to 13 metals in the art, preferably Pd or Rh, such as Pd; the salts of the group 3 to 13 metals can be Pd(OAc)2, Pd(dba)2 or Rh(acac)(CO)2, such as Pd(dba)2.

[0092] In the catalyst composition, the molar ratio of the compound represented by Formula I or Formula II to the metals of Groups 3 to 13 can be a conventional molar ratio in the art, or it can be 1:1 to 4:1 (e.g., 2:1).

[0093] In one embodiment, the catalyst composition may be Pd(dba)2 and

[0094]

[0095]

[0096]

[0097]

[0098]

[0099] or Metal complexes and / or mixtures formed.

[0100] The present invention also provides the use of compounds of formula I or II as described above in catalytic asymmetric organic synthesis reactions. In the described application, the compounds of formula I or II serve as chiral ligands.

[0101] In some embodiments, the asymmetric organic synthesis reaction is preferably a palladium-catalyzed asymmetric Sonogashira reaction or a palladium-catalyzed asymmetric Heck reaction.

[0102] In some embodiments, the asymmetric organic synthesis reaction is preferably a palladium-catalyzed asymmetric Sonogashira reaction of olefins or a palladium-catalyzed asymmetric Heck reaction.

[0103] In some embodiments, the asymmetric organic synthesis reaction is more preferably a palladium-catalyzed asymmetric Sonogashira reaction for constructing axially chiral olefins and / or a palladium-catalyzed asymmetric Heck reaction for constructing axially chiral olefins.

[0104] In some embodiments, the palladium-catalyzed asymmetric Heck reaction in the described application includes the following scheme:

[0105] Option 1 includes the following steps:

[0106] In a solvent, in the presence of a palladium catalyst, a compound as shown in Formula I or Formula II as described above, and a base, a compound as shown in Formula VI and a compound as shown in Formula VII are subjected to an asymmetric Heck reaction to give a compound as shown in Formula VIII.

[0107] ;

[0108] Among them, Ar is independently C6-C 14 Aromatic rings, surrounded by one or more R 13d Replacement C6-C 14 Aryl or 5-10 membered heteroaromatic ring, wherein the heteroatom in the 5-10 membered heteroaromatic ring is selected from N, and the number of heteroatoms is 1-2;

[0109] R 13 H, halogen, C1-C4 alkyl, or with one or more R 13a Substituted C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkyl acyl, -OH, phenoxy substituted with one or more halogens, -N(R) 13b ) (R 13c C6-C 14 aryl, with one or more R 13d Replacement C6-C 14Aryl, 5-6 membered cycloalkyl, 3-6 membered heterocycloalkyl, C1-C4 alkyl-OC(=O)-, N(R) 13f (R) 13g )-C(=O)- or by one or more R 13e Substituted 5-6 membered heterocyclic alkyl groups;

[0110] R 13a Independently, it is a C1-C4 alkoxy or C1-C4 alkyl-OC(=O)-;

[0111] R 13b and R 13c It is independently a C1-C4 alkyl or a C1-C4 alkyl acyl group;

[0112] R 13d Independently, it is a C1-C4 alkyl group;

[0113] R 13e It is an oxygen group independently;

[0114] R 13f and R 13g Independently H or C1-C4 alkyl;

[0115] R 14 It is H, halogen, nitro, C1-C4 alkyl, or C1-C4 alkyl substituted with one or more halogens.

[0116] In Scheme 1, the palladium catalyst can be Pd(OAc)2 or Pd(dba)2, preferably Pd(dba)2.

[0117] In Scheme 1, the compound represented by Formula I or Formula II is preferably any one of the following compounds:

[0118]

[0119]

[0120]

[0121]

[0122]

[0123]

[0124] .

[0125] In Scheme 1, the base can be a commonly used base for this type of reaction, preferably an organic base. The organic base can be DIPEA or triethylamine, preferably DIPEA.

[0126] In Scheme 1, the solvent can be a commonly used solvent for this type of reaction, preferably an aromatic solvent, an alcohol solvent, or an ether solvent, more preferably an alcohol solvent. The alcohol solvent can be one or more of tert-amyl alcohol, hexafluoroisopropanol, benzyl alcohol, trifluoroethanol, ethanol, and tert-butanol; preferably tert-butanol and / or tert-amyl alcohol, more preferably tert-amyl alcohol.

[0127] In the first embodiment, the molar ratio of the compound represented by Formula I or Formula II to the compound represented by Formula VI can be a conventional molar ratio for such reactions in the art, preferably 1:5-1:100, more preferably 1:5-1:50, and even more preferably 1:5-1:20, for example 1:20.

[0128] In the first embodiment, the molar ratio of the compound shown in Formula VI to the palladium catalyst can be a conventional molar ratio for such reactions in the art, preferably 10:1-100:1, more preferably 30:1-50:1, for example 40:1.

[0129] In the first embodiment, the molar ratio of the compound shown in Formula VI to the compound shown in Formula VII can be a conventional molar ratio for such reactions in the art, preferably 1:1-1:5, more preferably 1:1-1:2, for example 1:1.

[0130] In the first embodiment, the molar ratio of the compound as shown in Formula VI to the base can be a conventional molar ratio for such reactions in the art, preferably 1:1-1:5, more preferably 1:1-1:3, for example 1:2.

[0131] In Scheme 1, the volume molar ratio of the solvent to the compound shown in Formula VI is 0.5 mL / mmol - 20 mL / mmol; preferably 5 mL / mmol - 15 mL / mmol, for example 10 mL / mmol.

[0132] In Scheme 1, the temperature for the asymmetric Heck reaction of the olefin is -10 to 100 °C. o C; the optimal range is 30-70. o C.

[0133] In the first embodiment, the reaction is preferably carried out under the protection of an inert gas. The inert gas can be any inert gas commonly used in this type of reaction in the art, preferably nitrogen or argon, and more preferably nitrogen.

[0134] In the first embodiment, the progress of the Heck reaction can be monitored by conventional means in the art (e.g., TLC, HPLC or LCMS), and the reaction endpoint is generally defined as the disappearance or cessation of the reaction of the compound shown in Formula VI.

[0135] In the first embodiment, the Heck reaction may further include the following steps: at room temperature, under an inert gas atmosphere, stirring the palladium catalyst, the compound represented by formula I or II, the compound represented by formula VI, the compound represented by formula VII, and the organic solvent, adding the base, and stirring at 70°C. o The reaction is carried out at C to obtain the compound shown in formula VIII.

[0136] In the first embodiment, the Heck reaction may further include the following post-processing step: after the reaction is complete, the metal is removed. The metal removal operation may be silica gel column separation.

[0137] The metal removal step may further include a separation and purification step. The separation and purification operation may be a preparative plate separation.

[0138] In some implementation schemes, Scheme 1 may preferably be the following:

[0139] In a solvent, in the presence of a palladium catalyst, a compound as shown in Formula I or Formula II as described above, and a base, a compound as shown in Formula VI-a is subjected to an asymmetric Heck reaction with a compound as shown in Formula VII to give a compound as shown in Formula VIIIa or VIIIb.

[0140] ;

[0141] m can be 0, 1, 2, 3, 4 or 5;

[0142] R 15 It is a C1-C4 alkyl group or two adjacent R groups 15 Together with the C and C bonds they are connected to, they form a benzene ring.

[0143] In some implementations, R 13 For C6-C 14 Aryl, C1-C4 alkyl-OC(=O)- or N(R) 13f (R) 13g )-C(=O)-.

[0144] In some implementations, R 13f and R 13g For H.

[0145] In some implementations, R 14It is H or a C1-C4 alkyl group substituted with one or more halogens.

[0146] In some embodiments, the compound represented by Formula VI is , or .

[0147] In some embodiments, the compound represented by formula VII is , , or .

[0148] In the first embodiment, when the compound shown in Formula I or Formula II is a compound shown in Formula Ia or Formula IIa, a compound shown in Formula VIIIa is obtained; when the compound shown in Formula I or Formula II is a compound shown in Formula Ib or Formula IIb, a compound shown in Formula VIIIb is obtained.

[0149] In some embodiments, the palladium-catalyzed asymmetric Sonogashira reaction in the described application includes the following scheme two:

[0150] In an organic solvent, in the presence of a palladium catalyst, a copper catalyst, a base, and the compound shown as Formula I or Formula II as described above, the compound shown as Formula VI-a and the compound shown as Formula X undergo an asymmetric Sonogashira reaction to obtain the compound shown as Formula IXa or Formula IXb.

[0151] ;

[0152] Among them, R 12 The land is H, C1-C 14 alkyl, by one or more R 12a Substituted C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkyl acyl, -OH, phenoxy substituted with one or more halogens, -N(R) 12b (R) 12c C6-C 14 aryl, with one or more R 12d Replacement C6-C 14 aryl, 5-6 membered cycloalkyl, 3-6 membered heterocycloalkyl, or compounded by one or more R 12e Substituted 5-6 membered heterocyclic alkyl groups;

[0153] R 12a Independently, it is a C1-C4 alkoxy or C1-C4 alkyl-OC(=O)-;

[0154] R 12b and R 12cIt is independently a C1-C4 alkyl or a C1-C4 alkyl acyl group;

[0155] R 12d Independently, it is a C1-C4 alkyl group;

[0156] R 12e It is an oxygen group independently;

[0157] R 14 R 15 And m can be any of the above schemes.

[0158] In some implementations, R 12 For H, C1-C 14 Alkyl or C6-C 14 Aryl.

[0159] In some implementations, R 12 It is a phenyl group.

[0160] In the second embodiment, when the compound shown in Formula I or Formula II is a compound shown in Formula Ia or Formula IIa, a compound shown in Formula IXa is obtained; when the compound shown in Formula I or Formula II is a compound shown in Formula Ib or Formula IIb, a compound shown in Formula IXb is obtained.

[0161] In the second embodiment, the palladium catalyst can be Pd(OAc)2 or Pd(dba)2, preferably Pd(dba)2.

[0162] In the second embodiment, the compound represented by formula I or formula II is preferably any one of the following compounds:

[0163]

[0164]

[0165] .

[0166] In the second embodiment, the molar ratio of the compound shown in formula VI-a to the compound shown in formula X can be a conventional molar ratio for such reactions in the art, preferably 1:(1-5), more preferably 1:3.

[0167] In the second embodiment, the molar ratio of the compound shown in formula VI-a to the compound shown in formula I or II can be a conventional molar ratio for such reactions in the art, preferably 1:(0.01-0.5), more preferably 1:(0.05-0.2), for example 1:0.1.

[0168] In the second embodiment, the molar ratio of the compound shown in Formula VI-a to the palladium catalyst can be a conventional molar ratio for such reactions in the art, preferably 1:(0.01-0.5), more preferably 1:(0.01-0.1), for example 1:0.05.

[0169] In the second embodiment, the molar ratio of the compound shown in Formula VI-a to the copper catalyst can be a conventional molar ratio for such reactions in the art, preferably 1:(0.01-0.5), more preferably 1:(0.05-0.2), for example 1:0.1.

[0170] In the second embodiment, the molar ratio of the compound shown in formula VI-a to the base can be a conventional molar ratio for such reactions in the art, preferably 1:(1-5), more preferably 1:(3-4), for example 1:3.5.

[0171] In the second embodiment, the base can be a commonly used base in this type of reaction, preferably an organic base. The organic base can be DIPEA or triethylamine, preferably triethylamine.

[0172] In the second embodiment, the copper catalyst can be a commonly used copper catalyst in this type of reaction, preferably CuI.

[0173] In the second embodiment, the reaction is preferably carried out under the protection of an inert gas. The inert gas can be any inert gas commonly used in this type of reaction in the art, preferably nitrogen or argon, and more preferably nitrogen.

[0174] In the second embodiment, the solvent can be a conventional solvent for this type of reaction in the art, preferably an aromatic solvent or an ether solvent, more preferably an ether solvent. The aromatic solvent is preferably toluene. The ether solvent can be one or more of tetrahydrofuran, diethyl ether, n-butyl ether, and 1,4-dioxane; preferably tetrahydrofuran.

[0175] In the second scheme, the temperature of the Sonogashira reaction can be -10 to 100°C. o C; the optimal range is 30-70. o C, for example, 70 o C.

[0176] In the second embodiment, the progress of the Sonogashira reaction can be monitored by conventional means in the art (e.g., TLC, HPLC or LCMS), and the reaction endpoint is generally defined as the disappearance or cessation of the reaction of the compound shown in Formula VI-a.

[0177] In the second embodiment, the Sonogashira reaction may further include the following steps: at room temperature, under an inert gas atmosphere, stirring the palladium catalyst, the compound of formula I or II, and the organic solvent; adding the compound of formula VI, the base, and the compound of formula X; stirring; adding the copper catalyst; and then stirring at 70°C. o The reaction is carried out at C to obtain the compound represented by formula IX.

[0178] In Scheme 2, the Sonogashira reaction may further include the following post-processing step: after the reaction is complete, the metal is removed. The metal removal operation may be silica gel column separation.

[0179] The metal removal step may further include a separation and purification step. The separation and purification operation may be a preparative plate separation.

[0180] The present invention also provides a method for preparing a compound as shown in Formula I, comprising the following steps:

[0181] In an organic solvent, in the presence of a palladium catalyst, a phosphine ligand, a base, and a disubstituted phosphine oxide, the compound shown in Formula V-1 is subjected to reaction 1 as shown below to give the compound shown in Formula I.

[0182] ;

[0183] Among them, R 1 R 1’ R 2 R 2’ R 3 R 3’ R 4 R 4’ R 5 R 5’ The definitions of n1 and n2 are the same as described in any of the previous schemes.

[0184] In reaction 1, the organic solvent can be a conventional organic solvent in the art, preferably one or more of ether solvents (e.g., tetrahydrofuran, methyl tert-butyl ether, diethyl ether, ethylene glycol dimethyl ether, isopropyl ether, dioxane, n-butyl ether, petroleum ether, and n-butyl ether, and another example, tetrahydrofuran), halogenated hydrocarbon solvents (e.g., one or more of dichloromethane, chloroform, and 1,2-dichloroethane, and another example, dichloromethane), aromatic solvents (e.g., one or more of toluene, xylene, chlorobenzene, and trifluorotoluene, and another example, toluene), nitrile solvents (e.g., acetonitrile), alkane solvents (n-pentane and / or n-hexane), alcohol solvents (e.g., one or more of methanol, ethanol, isobutanol, and butanol), ketone solvents (e.g., acetone), amide solvents (e.g., N,N-dimethylformamide and / or N,N-dimethylacetamide), and sulfoxide solvents (e.g., dimethyl sulfoxide), preferably one or more of ether solvents, halogenated hydrocarbon solvents, aromatic solvents, and sulfoxide solvents, and more preferably sulfoxide solvents.

[0185] In reaction 1, the palladium catalyst can be a conventional palladium catalyst in the art, preferably one or more of palladium acetate, palladium chloride, palladium bromide, palladium iodide, palladium / carbon, palladium hydroxide, palladium oxide, palladium nitrate, palladium sulfate, ammonium chloropalladate, sodium chloropalladate, and potassium chloropalladate; more preferably palladium acetate.

[0186] In reaction 1, the phosphine ligand can be a conventional phosphine ligand in the art, preferably triphenylphosphine, trimethylphosphine, tricyclohexylphosphine, tri-tert-butylphosphine, di-tert-butylmethylphosphine, bis(dicyclohexylphosphine)methane, n-butyldi(1-adamantyl)phosphine, tris(p-tolyl)phosphine, tris(m-tolyl)phosphine, 2-(diphenylphosphino)-biphenyl, tris(3,5-xylyl)phosphine, tris(pentafluorophenyl)phosphine, tris(4-fluorophenyl)phosphine, tris(4-methoxyphenyl)phosphine Tris(3-methoxyphenyl)phosphine, tris(2,4,6-trimethoxyphenyl)phosphine, tris(4-trifluorotolyl)phosphine, tris[3,5-bis(trifluoromethyl)phenyl]phosphine, 2-diphenylphosphine-2'-methylbiphenyl, tris-2-furanylphosphine, diphenyl-2-pyridylphosphine, tris(2,6-dimethoxyphenyl)phosphine, diphenylmethylphosphine, tris(1-naphthyl)phosphine, cyclohexyldiphenylphosphine, dicyclohexylphenylphosphine, SPhos, XPhos tBuXPhos, DavePhos, BrettPhos, JohnPhos, MePhos, 2′-Dicyclohexylphosphine-2,4,6-trimethoxybiphenyl, RuPhos, PhDavePhos, 1,1′-bis(dicyclohexylphosphine)ferrocene, dppf, bis(diphenylphosphine)methane, 1,2-bis(biphenylphosphine)ethane, 1,3-bis(diphenylphosphine)propane, 1,4-bis(diphenylphosphine)propane One or more of the following: bis(diphenylphosphine)butane, 1,8-bis(diphenylphosphine)octane, Cy-DPEPhos, DPEPHos, XantPhos, 2,2'-bis(dicyclohexylphosphine)-1,1'-biphenyl, BINAP, SEGPHOS, DTBM-SEGPHOS, cis-1,2-bis(diphenylphosphine)ethylene, and 2,6-bis(di-tert-butylphosphinemethyl)pyridine; preferably 1,4-bis(diphenylphosphine)butane.

[0187] In reaction 1, the base can be a conventional base in the art, preferably an organic base or an inorganic base. The organic base can be one or more of pyridine, triethylamine, tributylamine, N-methylmorpholine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, triethylenediamine, N,N-diisopropylethylamine, N,O-bis(trimethylsilyl)acetamide, n-butyllithium, sec-butyllithium, tert-butyllithium, sodium di(trimethylsilyl)amino, lithium di(trimethylsilyl)amino, potassium di(trimethylsilyl)amino, sodium methoxide, proton sponge, potassium tert-butoxide, and sodium tert-butoxide. The inorganic base can be one or more of cesium carbonate, potassium carbonate, potassium phosphate, potassium acetate, sodium hydride, sodium hydroxide, and potassium hydroxide. The base is preferably N,N-diisopropylethylamine.

[0188] In reaction 1, the molar ratio of the compound shown in formula V-1 to the palladium catalyst can be a conventional molar ratio in the art, preferably 30:1-5:1, more preferably 25:1-15:1 (e.g., 20:1).

[0189] In reaction 1, the molar ratio of the compound as shown in formula V-1 to the phosphine ligand can be a conventional molar ratio in the art, preferably 30:1-5:1, more preferably 20:1-10:1 (50:3).

[0190] In reaction 1, the molar ratio of the compound as shown in formula V-1 to the base can be a conventional molar ratio in the art, preferably 1:1 to 1:20, more preferably 1:2 to 1:3 (e.g., 1:4).

[0191] In reaction 1, the molar ratio of the compound as shown in formula V-1 to the disubstituted phosphine oxide can be a conventional molar ratio in the art, preferably 1:1 to 1:10, more preferably 1:4 to 1:6 (e.g., 1:5).

[0192] In reaction 1, the molar concentration of the compound represented by formula V-1 in the organic solvent can be a conventional molar concentration in the art, preferably 0.05-1 mol / L, more preferably 0.1-0.5 mol / L (e.g., 0.1 mol / L).

[0193] The reaction 1 is preferably carried out in the presence of an inert gas. The inert gas is preferably nitrogen or argon, more preferably nitrogen.

[0194] The preparation method of the compound shown in Formula I may further include the following steps: in an organic solvent, in the presence of trichlorosilane and a base, the compound shown in Formula IV-1 is subjected to reaction 2 as shown below to obtain the compound shown in Formula V-1.

[0195] .

[0196] In reaction 2, the organic solvent can be a conventional organic solvent in the art, preferably an ether solvent (e.g., one or more of tetrahydrofuran, methyl tert-butyl ether, diethyl ether, ethylene glycol dimethyl ether, isopropyl ether, dioxane, n-butyl ether, petroleum ether, and n-butyl ether, or tetrahydrofuran), a halogenated hydrocarbon solvent (e.g., one or more of dichloromethane, chloroform, and 1,2-dichloroethane, or dichloromethane), an aromatic solvent (e.g., one or more of toluene, xylene, chlorobenzene, and trifluorotoluene, or toluene), a nitrile solvent (e.g., acetonitrile), an alkane solvent (n-pentane and / or n-hexane), an alcohol solvent (e.g., one or more of methanol, ethanol, isobutanol, and butanol), a ketone solvent (e.g., acetone), an amide solvent (e.g., N,N-dimethylformamide and / or N,N-dimethylacetamide), and a sulfoxide solvent (e.g., dimethyl sulfoxide), preferably an aromatic solvent.

[0197] In reaction 2, the base can be a conventional base in the art, preferably an organic base or an inorganic base. The organic base can be one or more of pyridine, triethylamine, tributylamine, N-methylmorpholine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, triethylenediamine, N,N-diisopropylethylamine, N,O-bis(trimethylsilyl)acetamide, n-butyllithium, sec-butyllithium, tert-butyllithium, sodium di(trimethylsilyl)amino, lithium di(trimethylsilyl)amino, potassium di(trimethylsilyl)amino, sodium methoxide, proton sponge, potassium tert-butoxide, and sodium tert-butoxide. The inorganic base can be one or more of cesium carbonate, potassium carbonate, potassium phosphate, potassium acetate, sodium hydride, sodium hydroxide, and potassium hydroxide. N,N-diisopropylethylamine is preferred.

[0198] In reaction 2, the molar ratio of the base to the compound shown in formula IV-1 can be a conventional molar ratio in the art, preferably 300:1-10:1, more preferably 100:1-30:1, and even more preferably 100:1-70:1 (e.g., 82:1).

[0199] In reaction 2, the molar ratio of the trichlorosilane to the compound shown in formula IV-1 can be a conventional molar ratio in the art, preferably 200:1-10:1, more preferably 50:1-20:1 (e.g. 31.2:1).

[0200] In reaction 2, the molar concentration of the compound represented by formula IV-1 in the organic solvent can be a conventional molar concentration in the art, preferably 0.01-4 mol / L, more preferably 0.05-2 mol / L, and even more preferably 0.1-0.3 mol / L (e.g., 0.2 mol / L).

[0201] In reaction 2, the reaction temperature can be a conventional reaction temperature in the art, preferably -20-200℃, more preferably 0-120℃.

[0202] The reaction 2 is preferably carried out in the presence of an inert gas. The inert gas is preferably nitrogen or argon, more preferably nitrogen.

[0203] The preparation method of the compound shown in Formula I may further include the following steps: in an organic solvent, in the presence of a palladium catalyst, a phosphine ligand, a base and a disubstituted phosphine oxide, the compound shown in Formula III-1 is subjected to reaction 3 as shown below to obtain the compound shown in Formula IV-1.

[0204] .

[0205] In reaction 3, the organic solvent can be a conventional organic solvent in the art, or it can be an ether solvent (e.g., one or more of tetrahydrofuran, methyl tert-butyl ether, diethyl ether, ethylene glycol dimethyl ether, isopropyl ether, dioxane, n-butyl ether, petroleum ether, and n-butyl ether, such as tetrahydrofuran), a halogenated hydrocarbon solvent (e.g., one or more of dichloromethane, chloroform, and 1,2-dichloroethane, such as dichloromethane), or an aromatic solvent (e.g., one or more of toluene, xylene, chlorobenzene, and trifluorotoluene, such as...). For example, one or more of the following solvents: toluene, nitrile solvents (e.g., acetonitrile), alkane solvents (n-pentane and / or n-hexane), alcohol solvents (e.g., one or more of methanol, ethanol, isobutanol and butanol), ketone solvents (e.g., acetone), amide solvents (e.g., N,N-dimethylformamide and / or N,N-dimethylacetamide), and sulfoxide solvents (e.g., dimethyl sulfoxide), preferably one or more of ether solvents, haloalkanes solvents, aromatic solvents, and sulfoxide solvents, more preferably sulfoxide solvents.

[0206] In reaction 3, the palladium catalyst can be a conventional palladium catalyst in the art, preferably one or more of palladium acetate, palladium chloride, palladium bromide, palladium iodide, palladium / carbon, palladium hydroxide, palladium oxide, palladium nitrate, palladium sulfate, ammonium chloropalladate, sodium chloropalladate, and potassium chloropalladate; more preferably palladium acetate.

[0207] In reaction 3, the phosphine ligand can be a conventional phosphine ligand in the art, preferably triphenylphosphine, trimethylphosphine, tricyclohexylphosphine, tri-tert-butylphosphine, di-tert-butylmethylphosphine, bis(dicyclohexylphosphine)methane, n-butyldi(1-adamantyl)phosphine, tris(p-tolyl)phosphine, tris(m-tolyl)phosphine, 2-(diphenylphosphino)-biphenyl, tris(3,5-xylyl)phosphine, tris(pentafluorophenyl)phosphine, tris(4-fluorophenyl)phosphine, tris(4-methoxyphenyl)phosphine Tris(3-methoxyphenyl)phosphine, tris(2,4,6-trimethoxyphenyl)phosphine, tris(4-trifluorotolyl)phosphine, tris[3,5-bis(trifluoromethyl)phenyl]phosphine, 2-diphenylphosphine-2'-methylbiphenyl, tris-2-furanylphosphine, diphenyl-2-pyridylphosphine, tris(2,6-dimethoxyphenyl)phosphine, diphenylmethylphosphine, tris(1-naphthyl)phosphine, cyclohexyldiphenylphosphine, dicyclohexylphenylphosphine, SPhos, XPhos tBuXPhos, DavePhos, BrettPhos, JohnPhos, MePhos, 2′-Dicyclohexylphosphine-2,4,6-trimethoxybiphenyl, RuPhos, PhDavePhos, 1,1'-bis(dicyclohexylphosphine)ferrocene, dppf, bis(diphenylphosphine)methane, 1,2-bis(biphenylphosphine)ethane, 1,3-bis(diphenylphosphine)propane, 1,4-bis(diphenylphosphine)propane One or more of the following: phosphine butane, 1,8-bis(diphenylphosphine)octane, Cy-DPEPhos, DPEPHos, XantPhos, 2,2'-bis(dicyclohexylphosphine)-1,1'-biphenyl, BINAP, SEGPHOS, DTBM-SEGPHOS, cis-1,2-bis(diphenylphosphine)ethylene, and 2,6-bis(di-tert-butylphosphinemethyl)pyridine; more preferably 1,4-bis(diphenylphosphine)butane.

[0208] In reaction 3, the base can be a conventional base in the art, preferably an organic base or an inorganic base. The organic base can be one or more of pyridine, triethylamine, tributylamine, N-methylmorpholine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, triethylenediamine, N,N-diisopropylethylamine, N,O-bis(trimethylsilyl)acetamide, n-butyllithium, sec-butyllithium, tert-butyllithium, sodium di(trimethylsilyl)amino, lithium di(trimethylsilyl)amino, potassium di(trimethylsilyl)amino, sodium methoxide, proton sponge, potassium tert-butoxide, and sodium tert-butoxide. The inorganic base can be one or more of cesium carbonate, potassium carbonate, potassium phosphate, potassium acetate, sodium hydride, sodium hydroxide, and potassium hydroxide. N,N-diisopropylethylamine is preferred.

[0209] In reaction 3, the molar ratio of the compound represented by formula III-1 to the palladium catalyst can be a conventional molar ratio in the art, preferably 30:1-5:1, more preferably 25:1-15:1 (e.g. 20:1).

[0210] In reaction 3, the molar ratio of the compound represented by formula III-1 to the phosphine ligand can be a conventional molar ratio in the art, preferably 30:1-5:1, more preferably 20:1-10:1 (e.g. 50:3).

[0211] In reaction 3, the molar ratio of the compound as shown in Formula III-1 to the base can be a conventional molar ratio in the art, preferably 1:1 to 1:20, more preferably 1:2 to 1:3 (e.g., 1:4).

[0212] In reaction 3, the molar ratio of the compound represented by formula III-1 to the disubstituted phosphine oxide can be a conventional molar ratio in the art, preferably 1:1-1:5, more preferably 1:1-1:2 (e.g. 1:1.3).

[0213] In reaction 3, the molar concentration of the compound represented by formula III-1 in the organic solvent can be a conventional molar concentration in the art, preferably 0.05-1 mol / L, more preferably 0.05-0.2 mol / L (e.g. 0.1 mol / L).

[0214] The reaction 3 is preferably carried out in the presence of an inert gas. The inert gas is preferably nitrogen or argon, more preferably nitrogen.

[0215] The present invention also provides a method for preparing a compound as shown in Formula II, comprising the following steps: in an organic solvent, in the presence of a palladium catalyst, a phosphine ligand, a base and a disubstituted phosphine oxide, the compound as shown in Formula V-2 is subjected to reaction 4 as shown below to obtain the compound as shown in Formula II;

[0216] ;

[0217] The organic solvent, palladium catalyst, phosphine ligand, base, disubstituted phosphine oxide, and reaction conditions can be any of the reaction 1 methods described in the preparation method of the compound shown in Formula I above.

[0218] R 6 R 6’ R 7 R 7’ R 8 R 8’ R 9 R 9’ R 10 R 10’ R 11 R 11’ The definitions of n3 and n4 are the same as those described in any previous scheme.

[0219] The preparation method of the compound shown in Formula II may further include the following steps: in an organic solvent, in the presence of trichlorosilane and a base, the compound shown in Formula IV-2 is subjected to the following reaction 5 to obtain the compound shown in Formula V-2.

[0220] ;

[0221] Wherein, the organic solvent, trichlorosilane, base and reaction conditions can be any of the schemes in reaction 2 of the preparation method of the compound shown in Formula I above;

[0222] R 6 R 6’ R 7 R 7’ R 8 R 8’ R 9 R 9’ R 10 R 10’ R 11 R 11’ The definitions of n3 and n4 are the same as those described in any previous scheme.

[0223] The preparation method of the compound shown in Formula II may further include the following steps: in an organic solvent, in the presence of a palladium catalyst, a phosphine ligand, a base and a disubstituted phosphine oxide, the compound shown in Formula III-2 is subjected to the following reaction 6 to obtain the compound shown in Formula IV-2.

[0224] ;

[0225] The organic solvent, palladium catalyst, phosphine ligand, base, disubstituted phosphine oxide, and reaction conditions can be any of the reaction 3 methods described in the preparation method of the compound shown in Formula I above.

[0226] R 6 R 6’ R 7 R 7’ R 8 R 8’ R 9 R 9’ R 10 R 10’ R 11 R 11’ The definitions of n3 and n4 are the same as those described in any previous scheme.

[0227] In this invention, unless otherwise specified, "room temperature" refers to 10-40°C. "°C" refers to degrees Celsius. "h" refers to hours.

[0228] Terminology Definition

[0229] Unless otherwise stated, the following terms and phrases used herein are intended to have the following meanings. A particular term or phrase should not be considered uncertain or unclear unless specifically defined, but should be understood in its ordinary sense.

[0230] The statement "group B is replaced by one or more groups A" means that one or more hydrogen atoms in group B are independently replaced by group A. When multiple groups A appear simultaneously, unless otherwise specified, their definitions are independent and do not affect each other. For example, "C6-C substituents with three halogens..."10 "Aromatic" refers to C6-C 10 The aryl group will be replaced by three halogens, the definitions of which are independent and do not affect each other, including but not limited to: , wait.

[0231] The statement "group B may be substituted by one or more groups A" means that group B may be unsubstituted or may be substituted by one or more groups A.

[0232] " at the end of the structural fragment" This means that the structural segment is connected to the rest of the molecule through this site. For example, It refers to cyclohexyl.

[0233] The "-" at the end of a group indicates that the group is attached to the rest of the molecule through that site. For example, CH3-C(=O)- refers to an acetyl group.

[0234] The terms “comprising,” “including,” “having,” “containing,” or “involving,” and their other variations herein, are inclusive or open-ended and do not exclude other elements or method steps not listed. Those skilled in the art will understand that the foregoing term “comprising” encompasses the meaning of “consisting of.”

[0235] The term "one or more" refers to one, two, or three.

[0236] The term "halogen" refers to fluorine, chlorine, bromine, or iodine.

[0237] The term "alkyl" refers to a saturated monovalent hydrocarbon group that has a specified number of carbon atoms (e.g., C1-C6), is straight-chain or branched. Alkyl groups include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, etc.

[0238] The term "cycloalkyl" refers to a cyclic, saturated monovalent hydrocarbon group having a specified number of carbon atoms (e.g., C3-C7), and is monocyclic. Cycloalkyl groups include, but are not limited to: , , , wait.

[0239] The term "heterocyclic alkyl" refers to a cyclic, saturated monovalent group having a specified number of ring atoms (e.g., 3-10), a specified number of heteroatoms (e.g., 1, 2, or 3), and a specified type of heteroatom (one, two, or three of N, O, and S), and is monocyclic. Heterocyclic alkyl groups are attached to the rest of the molecule via carbon atoms or heteroatoms. Heterocyclic alkyl groups include, but are not limited to: , , , wait.

[0240] The term "oxo-group" refers to the =O group, where an oxygen atom replaces two hydrogen atoms on the same carbon atom; that is, a carbonyl group replaces a methylene group.

[0241] The term "alkoxy" refers to the group R. X -O-,R X The definition is the same as the term "alkyl". Alkoxy groups include, but are not limited to: methoxy, ethoxy, n-propoxy, isopropoxy, etc.

[0242] The term "aryl" refers to an aryl group having a specified number of carbon atoms (e.g., C6-C). 15 Aryl group is a cyclic, unsaturated monovalent hydrocarbon group, which can be monocyclic or polycyclic (e.g., two or three). When polycyclic, adjacent monocyclic rings share two atoms and one bond, and at least one ring is aromatic. The aryl group is attached to the rest of the molecule via an aromatic or non-aromatic ring. Aryl groups include, but are not limited to, phenyl, naphthyl, and... , wait.

[0243] The term "heteroaryl" refers to a cyclic, unsaturated monovalent group having a specified number of ring atoms (e.g., 5-14), a specified number of heteroatoms (e.g., 1, 2, or 3), and a specified type of heteroatom (one or more of N, O, and S). It can be monocyclic or polycyclic; when polycyclic, adjacent monocyclic rings share two atoms and one bond, and at least one ring is aromatic. Heteroaryl groups are attached to the rest of the molecule via carbon atoms or heteroatoms; they can be attached to the rest of the molecule via a ring with or without heteroatoms; or they can be attached to the rest of the molecule via an aromatic ring or a non-aromatic ring. Heteroaryl groups include, but are not limited to: , , , , , , , , , , wait.

[0244] Based on common knowledge in the field, the above-mentioned preferred conditions can be combined arbitrarily to obtain various preferred embodiments of the present invention.

[0245] The reagents and raw materials used in this invention are all commercially available.

[0246] The significant advantages of this invention are as follows: the chiral spirobis(dihydrobenzothiophosphine-phosphine oxide) and chiral silicospirotetrahydronaphthylphosphine-phosphine oxide compounds of this invention, as chiral ligands, are characterized by simple synthesis and easy purification. These compounds can form metal complexes or mixtures with group III to thirteenth metal salts for catalyzing asymmetric organic synthesis reactions, exhibiting high catalytic activity and high enantioselectivity of products, and possessing the potential to enhance catalytic reaction activity. Especially in palladium-catalyzed asymmetric Heck reactions and / or Sonogashira reactions, they demonstrate excellent enantioselectivity and catalytic activity. Detailed Implementation

[0247] The present invention is further illustrated below by way of embodiments, but the invention is not limited to the scope of the embodiments described herein. Experimental methods in the following embodiments that do not specify specific conditions were performed according to conventional methods and conditions, or as selected according to the product instructions.

[0248] Example 1: Synthesis of Compound I-1

[0249]

[0250] Under nitrogen protection, spirobis(dihydrobenzothiophene) chiral bisphenol II-1 (6.89 g, 25.7 mmol), dichloromethane (128.5 mL), and pyridine (8.93 g, 113.1 mmol) were added to a 500 mL dry three-necked flask. The flask was then placed in an ice bath, and trifluoromethanesulfonic anhydride (16.7 g, 59.1 mmol) was slowly added dropwise. After the addition was complete, the mixture was stirred for 10 minutes, then the flask was removed from the ice bath, and the reaction system was allowed to return to room temperature (25 °C). o C) Stirring. The reaction was monitored by TLC until complete. The solvent was removed using a rotary evaporator. Ethyl acetate was added, and the mixture was washed successively with saturated sodium bicarbonate aqueous solution and saturated brine. The organic phase was dried over anhydrous sodium sulfate, filtered, and purified by column chromatography after solvent removal using a rotary evaporator to obtain III-1 (10.3 g, yield: 75%).

[0251]

[0252] White solid 1 H NMR (400 MHz, CDCl3) δ 7.44 (t, J = 7.8 Hz, 2H), 7.36–7.32(m, 2H), 7.11 (d, J = 8.2 Hz, 2H), 3.47–3.39 (m, 2H), 3.34–3.22 (m, 2H),1.66–1.58 (m, 2H), 1.38–1.30 (m, 2H);13 C NMR (100 MHz, CDCl3) δ 158.3, 154.1,132.9, 128.1, 125.9, 118.9 (q, J = 320.7 Hz), 117.1, 31.5, 9.1; 19 F NMR (375MHz, CDCl3) δ -74.21; HRMS (ESI-TOF) m / z Calcd for C 18 H 14 F6O6S2Si [M] + :531.9905, found: 531.9908.

[0253]

[0254] Under nitrogen protection, chiral spirobis(dihydrobenzothiopyrrolidone) trifluoromethanesulfonate III-1 (5.32 g, 10 mmol), diphenylphosphine oxide (2.5 g, 13 mmol), palladium acetate (112.5 mg, 0.5 mmol), 1,4-bis(diphenylphosphine)butane (256 mg, 0.6 mmol), degassed dimethyl sulfoxide (100 mL), and N,N-diisopropylethylamine (5.2 g, 40 mmol) were added to a 250 mL dry sealing tube. The tube was sealed at 110 °C. o After heating in an oil bath for 11 hours, the mixture was cooled to room temperature. The reaction system was then extracted with ethyl acetate, and the solvent was removed by rotary evaporation followed by column chromatography purification to obtain IV-1 (4.5 g, yield: 77%).

[0255]

[0256] White solid 1 H NMR (400 MHz, CDCl3) δ 7.52 (dd, J = 10.4, 7.6 Hz, 2H), 7.44 (dd, J = 4.8 Hz, 2H), 7.40–7.25 (m, 4H), 7.24–7.11 (m, 6H), 7.05 (dd, J= 12.4, 7.2 Hz, 1H), 6.67 (t, J = 4.8 Hz, 1H), 3.78–3.58 (m, 1H), 3.47–3.29 (m, 1H), 3.28–3.07 (m, 2H), 1.98–1.88 (m, 1H), 1.49–1.39 (m, 1H), 1.23–1.07(m, 2H); 13C NMR (100 MHz, CDCl3) δ 154.5, 153.9, 148.0, 142.2, 139.2, 133.3,132.3, 131.9, 129.7, 129.1, 128.9, 128.3, 128.0, 126.8, 126.0, 125.5, 120.4,31.33, 31.27, 14.2; 31 P NMR (162 MHz, CDCl3) δ 30.2 (s); 19 F NMR (375 MHz, CDCl3) δ -74.27; HRMS (ESI-TOF) m / z Calcd for C 29 H 24 F3O4PSSi [M] + : 584.0854, found: 584.0862.

[0257]

[0258] Under nitrogen protection, chiral spirobis(dihydrobenzothiophene)diphenylmonophosphine oxide IV-1 (1.2 g, 2 mmol), toluene (10.0 mL), and N,N-diisopropylethylamine (21.2 g, 164 mmol) were added to a 250 mL dry three-necked flask. The flask was then placed in an ice bath, and trichlorosilane (8.46 g, 62.4 mmol) was added. After refluxing the reaction system for 10 hours, it was cooled to room temperature and placed in an ice bath. The mixture was diluted with diethyl ether, and the reaction was quenched dropwise with saturated sodium bicarbonate solution. The mixture was filtered through diatomaceous earth, and the filtrate was evaporated by rotary evaporation to remove most of the solvent. The filtrate was then extracted with ethyl acetate, and the organic phases were combined, dried over anhydrous sodium sulfate, and purified by column chromatography after further solvent removal using a rotary evaporator to obtain V-1 (1.0 g, yield: 88%).

[0259]

[0260] White solid 1H NMR (400 MHz, CDCl3) δ 8.44 (dd, J = 7.2 Hz, 1H), 7.72 (dd, J = 7.6 Hz, 1H), 7.37 (s, 1H), 7.38–7.33 (m, 2H), 7.36–7.28 (m, 6H),7.23–7.16 (m, 1H), 7.15–7.09 (m, 4H), 3.08 (dd, J = 7.6 Hz, 1H), 3.02 (dd, J= 7.6 Hz, 1H), 2.96 (dd, J = 8.8 Hz, 2H), 1.53 (dd, J = 7.6 Hz, 4H); 13 C NMR (100 MHz, CDCl3) δ 154.6, 153.9, 151.5, 148.0, 144.3, 137.0, 134.0, 130.0,129.1, 129.0, 128.4, 128.07, 128.05, 126.8, 125.5, 122.0, 120.4, 31.6, 31.3,14.4; 31 P NMR (162 MHz, CDCl3) δ -6.57 (s); 19 F NMR (375 MHz, CDCl3) δ -74.30;HRMS (ESI-TOF) m / z Calcd for C 29 H 24 F3O3PSSi [M] + : 568.0905, found: 568.1023.

[0261]

[0262] Under nitrogen protection, chiral spirobis(dihydrobenzothiophene) monophosphine compound V-1 (5.68 g, 10 mmol), diphenylphosphine oxide (10.1 g, 50 mmol), palladium acetate (112.5 mg, 0.5 mmol), 1,4-bis(diphenylphosphine)butane (256 mg, 0.6 mmol), degassed dimethyl sulfoxide (100 mL), and N,N-diisopropylethylamine (5.2 g, 40 mmol) were added to a 250 mL dry sealed tube. The tube was sealed at 110 °C. o After heating in an oil bath for 10 hours, the mixture was cooled to room temperature. The reaction system was then extracted with ethyl acetate, and the solvent was removed by rotary evaporation followed by column chromatography purification to obtain IV-1 (5.0 g, yield: 95%).

[0263]

[0264] White solid 1 H NMR (400 MHz, CDCl3) δ 7.53 (t, J = 12.0, 7.6 Hz, 2H), 7.45 (d, J = 7.2 Hz, 2H), 7.38 (t, J = 6.0 Hz, 2H), 7.32–7.12 (m, 8H), 7.13–6.99 (m, 7H), 6.94 (dd, J = 12.8, 7.2 Hz, 1H), 6.89–6.74 (m, 3H), 3.66–3.56 (m, 2H), 3.29–3.02 (m, 2H), 1.47–1.37 (m, 1H), 1.20–1.07 (m, 1H), 1.07–0.78 (m, 2H); 13 C NMR (100 MHz, CDCl3) δ 157.7, 157.5, 155.2, 155.0, 147.9, 147.4, 142.1, 142.1, 142.0, 141.9, 140. 9, 140.8, 139.2, 139.1, 137.6, 137.5, 137.5, 136.4, 134.4, 133.7, 133.5, 133.4, 132.9, 132.7, 132.4, 132.0, 131.9, 131.8, 131.3, 131.3, 131.09, 131.06, 130.5, 130.4, 130.2, 130.1, 129.5, 129.40, 129.37, 128.7, 128.5, 128.3, 128.2, 128.1, 128.0, 127.84, 127.81, 127.77, 127.75, 127.70, 126.72, 32.5, 32.3 (d, J = 10 Hz), 11.3 (d, J = 3.7 Hz), 10.4.; 31 P NMR (162 MHz, CDCl3) δ 30.38 (s), -6.29 (s); HRMS (EI-TOF) m / z Calcd for C 40 H 34 OP2Si [M] + : 620.1854, found: 620.1855.

[0265] Following the same procedures and feed methods as in Example 1, and using the corresponding raw materials, compounds I-2 to I-210 were prepared.

[0266] Example 2: I-2

[0267]

[0268] White solid 1 H NMR (400 MHz, CDCl3) δ 7.53 (t, J = 12.0, 7.6 Hz, 2H), 7.45 (d, J = 7.2 Hz, 2H), 7.38 (t, J = 6.0 Hz, 2H), 7.32–7.12 (m, 8H), 7.13–6.99 (m, 7H), 6.94 (dd, J = 12.8, 7.2 Hz, 1H), 6.89–6.74 (m, 3H), 3.66–3.56 (m, 2H), 3.29–3.02 (m, 2H), 1.47–1.37 (m, 1H), 1.20–1.07 (m, 1H), 1.07–0.78(m, 2H); 13 C NMR (100 MHz, CDCl3) δ 157.7, 157.5, 155.2, 155.0, 147.9, 147.4,142.1, 142.1, 142.0, 141.9, 140.9, 140.8, 139.2, 139.1, 137.6, 137.5, 137.5,136.4, 134.4, 133.7, 133.5, 133.4, 132.9, 132.7, 132.4, 132.0, 131.9, 131.8,131.3, 131.3, 131.09, 131.06, 130.5, 130.4, 130.2, 130.1, 129.5, 129.40,129.37, 128.7, 128.5, 128.3, 128.2, 128.1, 128.0, 127.84, 127.81, 127.77,127.75, 127.70, 126.72, 32.5, 32.3 (d, J = 10 Hz), 11.3 (d, J = 3.7 Hz),10.4.; 31P NMR (162 MHz, CDCl3) δ 30.38 (s), -6.29 (s); HRMS (EI-TOF) m / zCalcd for C 40 H 34 OP2Si [M] + : 620.1854, found: 620.1854.

[0269] Example 3: I-3

[0270]

[0271] White solid 1 H NMR (400 MHz, CDCl3) δ 7.50–7.34 (m, 2H), 7.31 (d, J = 7.6Hz, 1H), 7.25 (dd, J = 7.6, 3.6 Hz, 4H), 7.22–7.18 (m, 2H), 7.15 (d, J = 8.0Hz, 2H), 7.13–7.15 (m, 2H), 6.99 (t, J = 7.2 Hz, 2H), 6.88 (dd, J = 7.2, 4.0Hz, 1H), 3.77–3.65 (m, 1H), 3.36–3.23 (m, 1H), 3.21–2.90 (m, 2H), 2.04–1.86(m, 2H), 1.86–1.59 (m, 5H), 1.59–1.31 (m, 8H), 1.31–1.11 (m, 3H), 1.11–0.66(m, 8H); 13C NMR (100 MHz, CDCl3) δ 157.7, 157.6, 155.4, 155.2, 148.0, 147.5,140.34, 140.27, 139.3, 139.2, 138.5, 138.3, 136.2, 135.3, 133.6, 133.4,133.1, 132.9, 130.5, 129.3, 128.72, 128.69, 128.6, 128.5, 128.12, 128.06,127.94, 127.92, 127.85, 127.5, 127.3, 127.0, 37.2, 36.5, 36.4, 35.8, 32.8,31.8 (d, J = 7.6 Hz), 26.6, 26.5, 26.4, 26.3, 26.0, 25.9, 25.7, 25.6, 25.13,25.10, 24.6, 11.8, 11.4 (d, J = 2.8 Hz); 31 P NMR (162 MHz, CDCl3) δ 46.22 (s),-6.59 (s); HRMS (EI-TOF) m / z Calcd for C 40 H 46 OP2Si [M] + : 632.2866, found: 632.2864

[0272] Example 4: I-4

[0273]

[0274] White solid 11H NMR (400 MHz, CDCl3) δ 7.50–7.34 (m, 2H), 7.31 (d, J = 7.6Hz, 1H), 7.25 (dd, J = 7.6, 3.6 Hz, 4H), 7.22–7.18 (m, 2H), 7.15 (d, J = 8.0Hz, 2H), 7.13–7.15 (m, 2H), 6.99 (t, J = 7.2 Hz, 2H), 6.88 (dd, J = 7.2, 4.0Hz, 1H), 3.77–3.65 (m, 1H), 3.36–3.23 (m, 1H), 3.21–2.90 (m, 2H), 2.04–1.86(m, 2H), 1.86–1.59 (m, 5H), 1.59–1.31 (m, 8H), 1.31–1.11 (m, 3H), 1.11–0.66(m, 8H); 13 13C NMR (100 MHz, CDCl3) δ 157.7, 157.6, 155.4, 155.2, 148.0, 147.5,140.34, 140.27, 139.3, 139.2, 138.5, 138.3, 136.2, 135.3, 133.6, 133.4,133.1, 132.9, 130.5, 129.3, 128.72, 128.69, 128.6, 128.5, 128.12, 128.06,127.94, 127.92, 127.85, 127.5, 127.3, 127.0, 37.2, 36.5, 36.4, 35.8, 32.8,31.8 (d, J = 7.6 Hz), 26.6, 26.5, 26.4, 26.3, 26.0, 25.9, 25.7, 25.6, 25.13,25.10, 24.6, 11.8, 11.4 (d, J = 2.8 Hz); 31 31P NMR (162 MHz, CDCl3) δ 46.22 (s), -6.59 (s); HRMS (EI-TOF) m / z Calcd for C 40 H 46 OP2Si [M] + : 632.2866, found: 632.2863.

[0275] Example 5: I-5

[0276]

[0277] White solid 1 H NMR (400 MHz, CDCl3) δ 7.72 (dd, J = 7.6 Hz, 1H), 7.43 (dt, J = 6.0 Hz, 1H), 7.41–7.30 (m, 4H), 7.34–7.27 (m, 4H), 7.24–7.16 (m, 2H), 7.15–7.09 (m, 4H), 3.00–2.92 (m, 3H), 2.88 (dd, J = 7.6 Hz, 1H), 1.51 (dd, J = 7.6 Hz, 4H), 0.96 (s, 18H); 13 C NMR (100 MHz, CDCl3) δ 154.3, 151.7,151.6, 149.2, 144.2, 137.0, 135.6, 134.0, 130.6, 130.0, 128.4, 128.07,128.05, 127.8, 122.0, 121.3, 64.4, 34.5, 31.9, 31.6, 30.2, 15.0; 31 P NMR (162MHz, CDCl3) δ 52.46 (s), -6.56 (s); HRMS (EI-TOF) m / z Calcd for C 36 H 42 OP2Si [M] + : 580.2480, found: 580.2482.

[0278] Example 6: I-6

[0279]

[0280] White solid 1H NMR (400 MHz, CDCl3) δ 7.72 (dd, J = 7.6 Hz, 1H), 7.43 (dt, J = 6.0 Hz, 1H), 7.41–7.30 (m, 4H), 7.34–7.27 (m, 4H), 7.24–7.16 (m, 2H), 7.15–7.09 (m, 4H), 3.00–2.92 (m, 3H), 2.88 (dd, J = 7.6 Hz, 1H), 1.51 (dd, J = 7.6 Hz, 4H), 0.96 (s, 18H); 13 C NMR (100 MHz, CDCl3) δ 154.3, 151.7,151.6, 149.2, 144.2, 137.0, 135.6, 134.0, 130.6, 130.0, 128.4, 128.07,128.05, 127.8, 122.0, 121.3, 64.4, 34.5, 31.9, 31.6, 30.2, 15.0; 31 P NMR (162MHz, CDCl3) δ 52.46 (s), -6.56 (s); HRMS (EI-TOF) m / z Calcd for C 36 H 42 OP2Si [M] + : 580.2480, found: 580.2481.

[0281] Example 7: I-7

[0282]

[0283] White solid 1H NMR (400 MHz, CDCl3) δ 7.44 (d, J = 7.6 Hz, 1H), 7.38 (td,J = 7.6, 3.2 Hz, 1H), 7.32 (d, J = 7.6 Hz, 1H), 7.29–7.23 (m, 4H), 7.23–7.12(m, 5H), 7.09 (ddd, J = 12.8, 6.4, 2.4 Hz, 2H), 6.98 (t, J = 7.6 Hz, 2H),6.88 (dd, J = 7.6, 4.0 Hz, 1H), 3.79–3.67 (m, 1H), 3.39–3.22 (m, 1H), 3.21–3.01 (m, 2H), 2.31–2.18 (m, 1H), 1.98–1.83 (m, 1H), 1.81–1.70 (m, 1H), 1.19(dd, J = 14.8, 7.2 Hz, 3H), 1.05 (dd, J = 14.8, 7.2 Hz, 3H), 1.00–0.81 (m,3H), 0.76 (dt, J = 15.6, 8.0 Hz, 6H); 13 C NMR (100 MHz, CDCl3) δ 157.8, 157.6,155.7, 155.6, 147.7, 147.2, 142.43, 142.41, 142.32, 142.30, 140.6, 140.5,139.2, 139.1, 138.1, 138.0, 136.5, 135.6, 133.6, 133.4, 133.1, 132.9, 130.67,130.66, 129.3, 128.82, 128.79, 128.6, 128.5, 128.14, 128.08, 128.01, 128.00,127.9, 127.4, 127.3, 127.0, 32.7, 31.9 (d, J = 7.1 Hz), 27.6, 27.0, 25.8,25.1, 16.3, 16.23, 16.20, 16.18, 15.53, 15.50, 15.40, 15.38, 15.36, 11.8,11.5 (d, J = 3.1 Hz); 31P NMR (162 MHz, CDCl3) δ 51.47 (s), -6.56 (s); HRMS(EI-TOF) m / z Calcd for C 34 H 38 OP2Si [M] + : 552.2240, found: 552.2238.

[0284] Example 8: I-8

[0285]

[0286] White solid 1 H NMR (400 MHz, CDCl3) δ 7.44 (d, J = 7.6 Hz, 1H), 7.38 (td,J = 7.6, 3.2 Hz, 1H), 7.32 (d, J = 7.6 Hz, 1H), 7.29–7.23 (m, 4H), 7.23–7.12(m, 5H), 7.09 (ddd, J = 12.8, 6.4, 2.4 Hz, 2H), 6.98 (t, J = 7.6 Hz, 2H), 6.88 (dd, J = 7.6, 4.0 Hz, 1H), 3.79–3.67 (m, 1H), 3.39–3.22 (m, 1H), 3.21–3.01 (m, 2H), 2.31–2.18 (m, 1H), 1.98–1.83 (m, 1H), 1.81–1.70 (m, 1H), 1.19 (dd, J = 14.8, 7.2 Hz, 3H), 1.05 (dd, J = 14.8, 7.2 Hz, 3H), 1.00–0.81 (m,3H), 0.76 (dt, J = 15.6, 8.0 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ 157.8, 157.6,155.7, 155.6, 147.7, 147.2, 142.43, 142.41, 142.32, 142.30, 140.6, 140.5,139.2, 139.1, 138.1, 138.0, 136.5, 135.6, 133.6, 133.4, 133.1, 132.9, 130.67,130.66, 129.3, 128.82, 128.79, 128.6, 128.5, 128.14, 128.08, 128.01, 128.00,127.9, 127.4, 127.3, 127.0, 32.7, 31.9 (d, J = 7.1 Hz), 27.6, 27.0, 25.8,25.1, 16.3, 16.23, 16.20, 16.18, 15.53, 15.50, 15.40, 15.38, 15.36, 11.8,11.5 (d, J = 3.1 Hz); 31 P NMR (162 MHz, CDCl3) δ 51.47 (s), -6.56 (s); HRMS(EI-TOF) m / z Calcd for C 34 H 38 OP2Si [M] + : 552.2240, found: 552.2237.

[0287] Example 9: I-9

[0288]

[0289] White solid 11H NMR (400 MHz, CDCl3) δ 7.61 (s, 1H), 7.47 (d, J = 7.6 Hz, 1H), 7.42 (s, 1H), 7.38–7.16 (m, 7H), 7.16–7.06 (m, 3H), 7.02 (t, J = 7.2 Hz, 2H), 6.88 (s, 1H), 6.83 (dd, J = 13.2, 6.0 Hz, 3H), 6.47–6.31 (m, 2H), 6.18–6.13 (m, 1H), 3.72–3.59 (m, 1H), 3.59–3.44 (m, 1H), 3.29–3.05 (m, 2H), 1.75–1.63 (m, 1H), 1.17–1.08 (m, 1H), 1.08–0.96 (m, 2H); 13 13C NMR (100 MHz, CDCl3) δ 157.4, 157.3, 155.5, 155.3, 149.5, 148.2, 148.10, 148.05, 148.0, 147.7, 147.6, 147.2, 146.8, 146.7, 142.0, 142.0, 141.9, 141.8, 141.2, 141.1, 138.9, 138.8, 137.7, 137.6, 135.1, 133.9, 133.6, 133.4, 133.1, 132.9, 130.5, 1,30.1, 130.0, 129.6, 129.5, 129.4, 129.1, 128.9, 128.2, 128.1, 127.9, 127.8, 127.7, 126.6, 122.8, 122.6, 122.3, 122.1, 110.62, 110.57, 110.53, 110.48, 32.4, 32.2 (d, J = 9.0 Hz), 11.1 (d, J = 3.8 Hz), 10.6; 31 31P NMR (162 MHz, CDCl3) δ 3.93 (s), -6.33 (s); HRMS (EI-TOF) m / z Calcd for C 36 14 30 18O3P2Si [M]+ + : 600.1512, found: 600.1514.

[0290] Example 10: I-10

[0291]

[0292] White solid 1 H NMR (400 MHz, CDCl3) δ 7.61 (s, 1H), 7.47 (d, J = 7.6 Hz,1H), 7.42 (s, 1H), 7.38–7.16 (m, 7H), 7.16–7.06 (m, 3H), 7.02 (t, J = 7.2 Hz,2H), 6.88 (s, 1H), 6.83 (dd, J = 13.2, 6.0 Hz, 3H), 6.47–6.31 (m, 2H), 6.18–6.13 (m, 1H), 3.72–3.59 (m, 1H), 3.59–3.44 (m, 1H), 3.29–3.05 (m, 2H), 1.75–1.63 (m, 1H), 1.17–1.08 (m, 1H), 1.08–0.96 (m, 2H); 13 C NMR (100 MHz, CDCl3) δ157.4, 157.3, 155.5, 155.3, 149.5, 148.2, 148.10, 148.05, 148.0, 147.7,147.6, 147.2, 146.8, 146.7, 142.0, 142.0, 141.9, 141.8, 141.2, 141.1, 138.9,138.8, 137.7, 137.6, 135.1, 133.9, 133.6, 133.4, 133.1, 132.9, 130.5, 130.1,130.0, 129.6, 129.5, 129.4, 129.1, 128.9, 128.2, 128.1, 127.9, 127.8, 127.7,126.6, 122.8, 122.6, 122.3, 122.1, 110.62, 110.57, 110.53, 110.48, 32.4, 32.2(d, J = 9.0 Hz), 11.1 (d, J = 3.8 Hz), 10.6; 31 P NMR (162 MHz, CDCl3) δ 3.93(s), -6.33 (s); HRMS (EI-TOF) m / z Calcd for C 36 H 30 O3P2Si [M]+ : 600.1512, found: 600.1515.

[0293] Example 11: I-11

[0294]

[0295] White solid 1 H NMR (400 MHz, CDCl3) δ 7.51–7.33 (m, 3H), 7.33–7.14 (m,9H), 7.10 (t, J = 7.6 Hz, 4H), 7.03–6.89 (m, 3H), 6.84 (s, 5H), 3.71–3.41 (m,2H), 3.30–2.93 (m, 2H), 2.37 (s, 3H), 2.22 (s, 3H), 1.57–1.43 (m, 1H), 1.16–1.05 (m, 1H), 1.05–0.81 (m, 2H); 13 C NMR (100 MHz, CDCl3) δ 157.6, 157.5,155.2, 155.1, 147.7, 147.4, 141.9, 141.9, 141.79, 141.76, 141.60, 141.57,141.2, 141.1, 141.0, 140.9, 139.4, 139.3, 138.2, 137.7, 137.6, 137.2, 133.9,133.7, 132.9, 132.7, 131.99, 131.97, 131.89, 131.87, 131.42, 130.39, 130.31,130.25, 130.2, 129.3, 129.24, 129.22, 129.0, 128.9, 128.7, 128.6, 128.52,128.46, 128.11, 128.05, 127.90, 127.86, 127.8, 127.74, 126.72, 32.5, 32.4 (d,J = 10.3 Hz), 21.54, 21.52, 21.50, 11.3 (d,J = 3.6 Hz), 10.5; 31 P NMR (162MHz, CDCl3) δ 30.49 (s), -6.33 (s); HRMS (EI-TOF) m / z Calcd for C 42 H 38OP2Si [M] + : 648.2240, found: 648.2234.

[0296] Example 12: I-12

[0297]

[0298] White solid 1 H NMR (400 MHz, CDCl3) δ 7.51–7.33 (m, 3H), 7.33–7.14 (m,9H), 7.10 (t, J = 7.6 Hz, 4H), 7.03–6.89 (m, 3H), 6.84 (s, 5H), 3.71–3.41 (m,2H), 3.30–2.93 (m, 2H), 2.37 (s, 3H), 2.22 (s, 3H), 1.57–1.43 (m, 1H), 1.16–1.05 (m, 1H), 1.05–0.81 (m, 2H); 13 C NMR (100 MHz, CDCl3) δ 157.6, 157.5,155.2, 155.1, 147.7, 147.4, 141.9, 141.9, 141.79, 141.76, 141.60, 141.57,141.2, 141.1, 141.0, 140.9, 139.4, 139.3, 138.2, 137.7, 137.6, 137.2, 133.9,133.7, 132.9, 132.7, 131.99, 131.97, 131.89, 131.87, 131.42, 130.39, 130.31,130.25, 130.2, 129.3, 129.24, 129.22, 129.0, 128.9, 128.7, 128.6, 128.52,128.46, 128.11, 128.05, 127.90, 127.86, 127.8, 127.74, 126.72, 32.5, 32.4 (d,J = 10.3 Hz), 21.54, 21.52, 21.50, 11.3 (d,J = 3.6 Hz), 10.5; 31 P NMR (162MHz, CDCl3) δ 30.49 (s), -6.33 (s); HRMS (EI-TOF) m / z Calcd for C 42H 38 OP2Si [M] + : 648.2240, found: 648.2235.

[0299] Example 13: I-13

[0300]

[0301] White solid 1 H NMR (400 MHz, CDCl3) δ 7.45 (t, J = 8.4 Hz, 3H), 7.35–7.14(m, 7H), 7.11 (t, J = 7.2 Hz, 4H), 7.01–6.73 (m, 8H), 6.51 (d, J = 6.8 Hz, 2H), 3.80 (s, 3H), 3.65 (s, 3H), 3.63–3.50 (m, 2H), 3.27–3.00 (m, 2H), 1.66–1.51 (m, 1H), 1.15–1.04 (m, 1H), 1.04–0.80 (m, 2H); 13 C NMR (100 MHz, CDCl3) δ161.90, 161.87, 161.50, 161.47, 157.6, 157.5, 155.3, 155.1, 147.9, 147.3,141.84, 141.81, 141.69, 141.66, 141.0, 140.9, 139.4, 139.2, 138.7, 137. 8,137.7, 137.6, 133.9, 133.7, 133.71, 133.69, 133.63, 133.60, 132.8, 132.7,130.4, 130.3, 130.1, 129.3, 129.22, 129.19, 128.7, 128.5, 128.1, 128.03,127.95, 127.9, 127.8, 127.71, 126.70, 126.1, 125.0, 124.8, 123.7, 113.8,113.7, 113.3, 113.2, 55.2, 54.9, 32.5, 32.3 (d, J = 10.2 Hz), 11.2 (d, J =3.7 Hz), 10.5; 31P NMR (162 MHz, CDCl3) δ 30.07 (s), -6.36 (s); HRMS (EI-TOF)m / z Calcd for C 42 H 38 O3P2Si [M] + : 680.2065, found: 680.2068.

[0302] Example 14: I-14

[0303]

[0304] White solid 1 H NMR (400 MHz, CDCl3) δ 7.45 (t, J = 8.4 Hz, 3H), 7.35–7.14(m, 7H), 7.11 (t, J = 7.2 Hz, 4H), 7.01–6.73 (m, 8H), 6.51 (d, J = 6.8 Hz, 2H), 3.80 (s, 3H), 3.65 (s, 3H), 3.63–3.50 (m, 2H), 3.27–3.00 (m, 2H), 1.66–1.51 (m, 1H), 1.15–1.04 (m, 1H), 1.04–0.80 (m, 2H); 13C NMR (100 MHz, CDCl3) δ161.90, 161.87, 161.50, 161.47, 157.6, 157.5, 155.3, 155.1, 147.9, 147.3,141.84, 141.81, 141.69, 141.66, 141.0, 140.9, 139.4, 139.2, 138.7, 137. 8,137.7, 137.6, 133.9, 133.7, 133.71, 133.69, 133.63, 133.60, 132.8, 132.7,130.4, 130.3, 130.1, 129.3, 129.22, 129.19, 128.7, 128.5, 128.1, 128.03,127.95, 127.9, 127.8, 127.71, 126.70, 126.1, 125.0, 124.8, 123.7, 113.8,113.7, 113.3, 113.2, 55.2, 54.9, 32.5, 32.3 (d, J = 10.2 Hz), 11.2 (d, J =3.7 Hz), 10.5; 31 P NMR (162 MHz, CDCl3) δ 30.07 (s), -6.36 (s); HRMS (EI-TOF)m / z Calcd for C 42 H 38 O3P2Si [M] + : 680.2065, found: 680.2067.

[0305] Example 15: I-15

[0306]

[0307] White solid 1H NMR (400 MHz, CDCl3) δ 7.64 (d, J = 7.2 Hz, 4H), 7.59 (d,J = 7.6 Hz, 2H), 7.49 (d, J = 8.0 Hz, 1H), 7.42 (q, J = 7.2 Hz, 6H), 7.38–7.29 (m, 3H), 7.29–7.20 (m, 5H), 7.20–6.98 (m, 10H), 6.88 (q, J = 7.6 Hz,3H), 3.74–3.54 (m, 2H), 3.32–3.01 (m, 2H), 1.71–1.58 (m, 1H), 1.18–1.05 (m,1H), 1.05–0.89 (m, 2H); 13 C NMR (100 MHz, CDCl3) δ 157.9, 157.7, 155.3, 155.2,147.5, 147.0, 144.1, 144.0, 143.49, 143.46, 142.12, 142.10, 141.98, 141.95,140.98, 140.91, 140.0, 139.90, 139.5, 139.3, 137.8, 137.6, 137.5, 136.7,134.0, 133.8, 133.1, 132.8, 132.6, 132.5, 132.38, 132.36, 132.3, 132.1,131.9, 130.9, 130.5, 130.3, 129.6, 129.54, 129.46, 128.9, 128.8, 128.7,128.6, 128.10, 128.06, 128.04, 127.96, 127.94, 127.87, 127.8, 127.7, 127.2,127.1, 127.0, 126.9, 126.7, 126.5, 126.4, 32.5, 32.3 (d, J = 10.3 Hz), 11.1(d, J = 4.0 Hz), 10.6; 31 P NMR (162 MHz, CDCl3) δ 30.51 (s), -6.30 (s); HRMS(EI-TOF) m / z Calcd for C 52 H 42 OP2Si [M] + : 772.2553, found: 772.2551.

[0308] Example 16: I-16

[0309]

[0310] White solid 1 H NMR (400 MHz, CDCl3) δ 7.64 (d, J = 7.2 Hz, 4H), 7.59 (d,J = 7.6 Hz, 2H), 7.49 (d, J = 8.0 Hz, 1H), 7.42 (q, J = 7.2 Hz, 6H), 7.38–7.29 (m, 3H), 7.29–7.20 (m, 5H), 7.20–6.98 (m, 10H), 6.88 (q, J = 7.6 Hz,3H), 3.74–3.54 (m, 2H), 3.32–3.01 (m, 2H), 1.71–1.58 (m, 1H), 1.18–1.05 (m,1H), 1.05–0.89 (m, 2H); 13 C NMR (100 MHz, CDCl3) δ 157.9, 157.7, 155.3, 155.2,147.5, 147.0, 144.1, 144.0, 143.49, 143.46, 142.12, 142.10, 141.98, 141.95,140.98, 140.91, 140.0, 139.90, 139.5, 139.3, 137.8, 137.6, 137.5, 136.7,134.0, 133.8, 133.1, 132.8, 132.6, 132.5, 132.38, 132.36, 132.3, 132.1,131.9, 130.9, 130.5, 130.3, 129.6, 129.54, 129.46, 128.9, 128.8, 128.7,128.6, 128.10, 128.06, 128.04, 127.96, 127.94, 127.87, 127.8, 127.7, 127.2,127.1, 127.0, 126.9, 126.7, 126.5, 126.4, 32.5, 32.3 (d, J = 10.3 Hz), 11.1(d, J = 4.0 Hz), 10.6; 31P NMR (162 MHz, CDCl3) δ 30.51 (s), -6.30 (s); HRMS(EI-TOF) m / z Calcd for C 52 H 42 OP2Si [M] + : 772.2553, found: 772.2552.

[0311] Example 17: I-17

[0312]

[0313] White solid 1 H NMR (400 MHz, CDCl3) δ 7.37 (dd, J = 16.0, 7.2 Hz, 3H), 7.24 (d, J = 7.2 Hz, 4H), 7.21–7.05 (m, 7H), 7.00 (dd, J = 12.4, 7.2 Hz, 1H), 6.92 (dd, J = 14.0. 8.8 Hz, 4H), 6.86 (dd, J = 7.2, 4.0 Hz, 1H), 6.64 (d, J =6.8 Hz, 2H), 6.23 (d, J = 6.8, 2.2 Hz, 2H), 3.64–3.51 (m, 2H), 3.25–3.01 (m,2H), 2.96 (s, 6H), 2.83 (s, 6H), 1.73–1.62 (m, 1H), 1.09–0.99 (m, 1H), 0.99–0.83 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 157.3, 157.1, 155.2, 155.0, 151.82,151.80, 151.44, 151.42, 148.4, 147.8, 141.49, 141.46, 141.34, 141.31, 140.83,140.76, 140.1, 139.5, 139.4, 139.0, 138.1, 138.0, 134.0, 133.8, 133.30,133.26, 133.19, 133.15, 132.9, 132.7, 130.4, 130.3, 129.1, 128.71, 128.69,128.5, 128.4, 128.1, 128.0, 127.9, 127.8, 127.74, 127.65, 126.6, 120.3,119.2, 119.0, 117.9, 111.1, 111.0, 110.7, 110.6, 39.9, 39.8, 32.5, 32.3 (d, J= 10.1 Hz), 11.3 (d, J = 3.5 Hz), 10.6; 31 P NMR (162 MHz, CDCl3) δ 31.36 (s),-6.21 (s); HRMS (EI-TOF) m / z Calcd for C 44 H 44 N2OP2Si [M] + : 706.2771, found:706.2763.

[0314] Example 18: I-18

[0315]

[0316] White solid 1H NMR (400 MHz, CDCl3) δ 7.37 (dd, J = 16.0, 7.2 Hz, 3H),7.24 (d, J = 7.2 Hz, 4H), 7.21–7.05 (m, 7H), 7.00 (dd, J = 12.4, 7.2 Hz, 1H),6.92 (dd, J = 14.0. 8.8 Hz, 4H), 6.86 (dd, J = 7.2, 4.0 Hz, 1H), 6.64 (d, J =6.8 Hz, 2H), 6.23 (d, J = 6.8, 2.2 Hz, 2H), 3.64–3.51 (m, 2H), 3.25–3.01 (m,2H), 2.96 (s, 6H), 2.83 (s, 6H), 1.73–1.62 (m, 1H), 1.09–0.99 (m, 1H), 0.99–0.83 (m, 2H); 13 C NMR (100 MHz, CDCl3) δ 157.3, 157.1, 155.2, 155.0, 151.82,151.80, 151.44, 151.42, 148.4, 147.8, 141.49, 141.46, 141.34, 141.31, 140.83,140.76, 140.1, 139.5, 139.4, 139.0, 138.1, 138.0, 134.0, 133.8, 133.30,133.26, 133.19, 133.15, 132.9, 132.7, 130.4, 130.3, 129.1, 128.71, 128.69,128.5, 128.4, 128.1, 128.0, 127.9, 127.8, 127.74, 127.65, 126.6, 120.3,119.2, 119.0, 117.9, 111.1, 111.0, 110.7, 110.6, 39.9, 39.8, 32.5, 32.3 (d, J= 10.1 Hz), 11.3 (d, J = 3.5 Hz), 10.6; 31 P NMR (162 MHz, CDCl3) δ 31.36 (s),-6.21 (s); HRMS (EI-TOF) m / z Calcd for C 44 H 44 N2OP2Si [M] +: 706.2771, found:706.2761.

[0317] Example 19: I-19

[0318]

[0319] White solid 1 H NMR (400 MHz, CDCl3) δ 7.50 (q, J = 8.4 Hz, 3H), 7.32 (td,J = 7.6, 3.6 Hz, 1H), 7.28–7.16 (m, 6H), 7.16–7.02 (m, 6H), 7.02–6.84 (m,4H), 6.80 (t, J = 7.6 Hz, 2H), 6.71 (t J = 6.4 Hz, 2H), 3.76–3.40 (m, 2H), 3.33–2.98 (m, 2H), 1.55–1.41 (m, 1H), 1.21–1.07 (m, 1H), 1.07–0.81 (m, 2H); 13 C NMR (100 MHz, CDCl3) δ 166.1, 166.0, 165.74, 165.71, 163.6, 163.5, 163.23,163.20, 158.1, 157.9, 155.3, 155.1, 147.5, 147.0, 142.33, 142.30, 142.18,142.15, 141.12, 141.05, 139.3, 139.2, 137.6, 137.5, 137.24, 136.15, 134.42,134.38, 134.34, 134.32, 134.29, 134.27, 134.23, 134.18, 134.0, 133.7, 132.8, 132.6, 130.6, 130.5, 130.4, 130.3, 130.2, 130.1, 129.81, 129.78, 129.6, 129.33, 129.29, 129.1, 129.0, 128.9, 128.7, 128.2, 128.1, 128.02, 127.97, 127.9, 127.8, 126.8, 115.9, 115.8, 115.7, 115.6, 115.4, 115.3, 115.2, 115.1, 32.5, 32.4, 32.3, 11.2, 11.1, 10.4;31 P NMR (162 MHz, CDCl3) δ 29.05 (s), -6.42 (s); 19 F NMR (375 MHz, CDCl3) δ -107.78, -108.05; HRMS (EI-TOF) m / z Calcdfor C 40 H 32 F2OP2Si [M] + : 656.1739, found: 656.1738.

[0320] Example 20: I-20

[0321]

[0322] White solid 1 H NMR (400 MHz, CDCl3) δ 7.50 (q, J = 8.4 Hz, 3H), 7.32 (td,J = 7.6, 3.6 Hz, 1H), 7.28–7.16 (m, 6H), 7.16–7.02 (m, 6H), 7.02–6.84 (m,4H), 6.80 (t, J = 7.6 Hz, 2H), 6.71 (t J = 6.4 Hz, 2H), 3.76–3.40 (m, 2H), 3.33–2.98 (m, 2H), 1.55–1.41 (m, 1H), 1.21–1.07 (m, 1H), 1.07–0.81 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 166.1, 166.0, 165.74, 165.71, 163.6, 163.5, 163.23,163.20, 158.1, 157.9, 155.3, 155.1, 147.5, 147.0, 142.33, 142.30, 142.18,142.15, 141.12, 141.05, 139.3, 139.2, 137.6, 137.5, 137.24, 136.15, 134.42,134.38, 134.34, 134.32, 134.29, 134.27, 134.23, 134.18, 134.0, 133.7, 132.8, 132.6, 130.6, 130.5, 130.4, 130.3, 130.2, 130.1, 129.81, 129.78, 129.6, 129.33, 129.29, 129.1, 129.0, 128.9, 128.7, 128.2, 128.1, 128.02, 127.97, 127.9, 127.8, 126.8, 115.9, 115.8, 115.7, 115.6, 115.4, 115.3, 115.2, 115.1, 32.5, 32.4, 32.3, 11.2, 11.1, 10.4; 31 P NMR (162 MHz, CDCl3) δ 29.05 (s), -6.42 (s); 19 F NMR (375 MHz, CDCl3) δ -107.78, -108.05; HRMS (EI-TOF) m / z Calcdfor C 40 H 32 F2OP2Si [M] + : 656.1739, found: 656.1736.

[0323] Example 21: I-21

[0324]

[0325] White solid 1H NMR (400 MHz, CDCl3) δ 7.52 (d, J = 7.6 Hz, 1H), 7.49–7.37(m, 4H), 7.33 (ddd, J = 14.8, 7.2, 3.2 Hz, 1H), 7.29–7.18 (m, 6H), 7.14 (t, J= 7.2 Hz, 2H), 7.08 (t, J = 6.8 Hz, 2H), 7.00 (d, J = 6.0 Hz, 2H), 6.97–6.85(m, 4H), 6.81 (t, J = 7.6 Hz, 2H), 3.75–3.42 (m, 2H), 3.34–3.00 (m, 2H),1.65–1.47 (m, 1H), 1.22–1.10 (m, 1H), 1.09–0.81 (m, 2H); 13 C NMR (100 MHz,CDCl3) δ 158.1, 158.0, 155.3, 155.1, 147.2, 146.6, 142.34, 142.31, 142.19,142.16, 141.12, 141.05, 139.3, 139.1, 138.19, 138.15, 137.84, 137.80, 137.4,137.3, 136. 7, 135.6, 133.9, 133.7, 133.3, 133.22, 133.18, 133.1, 133.0,132.73, 132.66, 132.6, 131.7, 131.3, 130.47, 130.45, 130.2, 130.1, 129.92,129.89, 129.6, 128.9, 128.8, 128.74, 128.66, 128.30, 128.25, 128.2, 128.12,128.06, 128.0, 127.92, 127.87, 127.8, 126.8, 32.4, 32.3, 11.0 (d, J = 3.8Hz), 10.4; 31 P NMR (162 MHz, CDCl3) δ 29.27 (s), -6.37 (s); HRMS (EI-TOF) m / zCalcd for C 40 H 32 Cl2OP2Si [M] + : 688.1148, found: 688.1145.

[0326] Example 22: I-22

[0327]

[0328] White solid 1 H NMR (400 MHz, CDCl3) δ 7.52 (d, J = 7.6 Hz, 1H), 7.49–7.37(m, 4H), 7.33 (ddd, J = 14.8, 7.2, 3.2 Hz, 1H), 7.29–7.18 (m, 6H), 7.14 (t, J= 7.2 Hz, 2H), 7.08 (t, J = 6.8 Hz, 2H), 7.00 (d, J = 6.0 Hz, 2H), 6.97–6.85(m, 4H), 6.81 (t, J = 7.6 Hz, 2H), 3.75–3.42 (m, 2H), 3.34–3.00 (m, 2H),1.65–1.47 (m, 1H), 1.22–1.10 (m, 1H), 1.09–0.81 (m, 2H); 13 C NMR (100 MHz, CDCl3) δ 158.1, 158.0, 155.3, 155.1, 147.2, 146.6, 142.34, 142.31, 142.19,142.16, 141.12, 141.05, 139.3, 139.1, 138.19, 138.15, 137.84, 137.80, 137.4,137.3, 136.7, 135.6, 133.9, 133.7, 133.3, 133.22, 133.18, 133.1, 133.0,132.73, 132.66, 132.6, 131.7, 131.3, 130.47, 130.45, 130.2, 130.1, 129.92,129.89, 129.6, 128.9, 128.8, 128.74, 128.66, 128.30, 128.25, 128.2, 128.12,128.06, 128.0, 127.92, 127.87, 127.8, 126.8, 32.4, 32.3, 11.0 (d, J = 3.8Hz), 10.4; 3131P NMR (162 MHz, CDCl3) δ 29.27 (s), -6.37 (s); HRMS (EI-TOF) m / zCalcd for C 40 H 32 Cl2OP2Si [M] + : 688.1148, found: 688.1144.

[0329] Example 23: I-23

[0330]

[0331] White solid, 1 1H NMR (400 MHz, CDCl3) 1 1H NMR (500 MHz, Chloroform-d) δ 8.17(dd, J = 5.2 Hz, 1H), 7.72 (dd, J = 7.6 Hz, 1H), 7.67 (dd, J = 7.2 Hz, 1H),7.51 (dq, J = 7.2 Hz, 1H), 7.41–7.34 (m, 2H), 7.36–7.28 (m, 5H), 7.23–7.16(m, 1H), 7.15–7.09 (m, 4H), 2.96 (dd, J = 8. 0 Hz, 4H), 1.46 (dd, J = 8.0 Hz,4H); 13 13C NMR (100 MHz, CDCl3) δ 159.9, 153.8, 151.6, 143. 8, 137.0, 136.1,135.4, 134.0, 130.4, 130.0, 129.2, 128.4, 128.07, 128.05, 125.8, 122.0,118.8, 31.6, 31.3, 14.7; 31 31P NMR (162 MHz, CDCl3) δ 24.60 (s), -6.45 (s); 19 19F NMR (375 MHz, CDCl3) δ -63.25; HRMS (EI-TOF) m / z Calcd for C 42 H 32 F6OP2Si [M] + :756.1602, found: 756.1605

[0332] Example 24: I-24

[0333]

[0334] White solid 1 H NMR (400 MHz, CDCl3) 1 H NMR (500 MHz, Chloroform-d) δ 8.17(dd, J = 5.2 Hz, 1H), 7.72 (dd, J = 7.6 Hz, 1H), 7.67 (dd, J = 7.2 Hz, 1H), 7.51 (dq, J = 7.2 Hz, 1H), 7.41–7.34 (m, 2H), 7.36–7.28 (m, 5H), 7.23–7.16(m, 1H), 7.15–7.09 (m, 4H), 2.96 (dd, J = 8. 0 Hz, 4H), 1.46 (dd, J = 8.0 Hz, 4H); 13 C NMR (100 MHz, CDCl3) δ 159.9, 153.8, 151.6, 143. 8, 137.0, 136.1, 135.4, 134.0, 130.4, 130.0, 129.2, 128.4, 128.07, 128.05, 125.8, 122.0,118.8, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 24.60 (s), -6.45 (s); 19 FNMR (375 MHz, CDCl3) δ -63.25; HRMS (EI-TOF) m / z Calcd for C 42 H 32 F6OP2Si [M] + :756.1602, found: 756.1604.

[0335] Example 25: I-25

[0336]

[0337] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8 Hz, 1H), 7.72 (dd, J = 7.6 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.56 (d, J = 1.6 Hz, 2H), 7.55 (d, J = 1.6 Hz, 2H), 7.53–7.48 (m, 1H), 7.39–7.35 (m, 4H), 7.35–7.33 (m,3H), 7.33–7.29 (m, 3H), 7.21–7.17 (m, 1H), 7.13 (d, J = 1.6 Hz, 2H), 7.12 (t,J = 1.6 Hz, 2H), 3.15–2.80 (m, 4H), 1.46 (ddd, J = 7.6 Hz, 4H), 1.35 (s,18H); 13 C NMR (100 MHz, CDCl3) δ 154.1, 153.9, 153.7, 151.6, 143.6, 142.2,138.0, 137.0, 134.0, 132.9, 131.7, 130.0, 128.9, 128.4, 128.07, 128.05,128.0, 126.1, 125.9, 122.0, 34.6, 31.6, 31.3, 31.2, 14.7; 31 P NMR (162 MHz, CDCl3) δ 29.11 (s), -6.49 (s); HRMS (EI-TOF) m / z Calcd for C 48 H 50 OP2Si [M] + :732.3106, found: 732.3111.

[0338] Example 26: I-26

[0339]

[0340] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8 Hz, 1H), 7.72 (dd, J = 7.6 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.56 (d, J = 1.6 Hz, 2H), 7.55 (d, J = 1.6 Hz, 2H), 7.53–7.48 (m, 1H), 7.39–7.35 (m, 4H), 7.35–7.33 (m,3H), 7.33–7.29 (m, 3H), 7.21–7.17 (m, 1H), 7.13 (d, J = 1.6 Hz, 2H), 7.12 (t,J = 1.6 Hz, 2H), 3.15–2.80 (m, 4H), 1.46 (ddd, J = 7.6 Hz, 4H), 1.35 (s,18H); 13 C NMR (100 MHz, CDCl3) δ 154.1, 153.9, 153.7, 151.6, 143.6, 142.2,138.0, 137.0, 134.0, 132.9, 131.7, 130.0, 128.9, 128.4, 128.07, 128.05,128.0, 126.1, 125.9, 122.0, 34.6, 31.6, 31.3, 31.2, 14.7; 31 P NMR (162 MHz, CDCl3) δ 29.11 (s), -6.49 (s); HRMS (EI-TOF) m / z Calcd for C 48 H 50 OP2Si [M] + :732.3106, found: 732.3110.

[0341] Example 27: I-27

[0342]

[0343] White solid 11H NMR (400 MHz, CDCl3) δ 7.41 (t, J = 8.4 Hz, 2H), 7.34–7.16(m, 9H), 7.16–6.93 (m, 9H), 6.89–6.77 (m, 2H), 6.72 (t, J = 7.6 Hz, 2H),3.78–3.39 (m, 2H), 3.28–3.00 (m, 2H), 2.31 (s, 3H), 2.13 (s, 3H), 1.51 (t, J= 11.2 Hz, 1H), 1.11–0.79 (m, 3H); 13 13C NMR (100 MHz, CDCl3) δ 157.6, 157.4,155.4, 155.3, 147.6, 147.0, 142.0, 141.9, 141.82, 141.79, 141.0, 140.9,139.1, 139.0, 138.0, 137.9, 137.9, 137.8, 137.5, 137.4, 136.8, 134.8, 133.8,133.6, 133.4, 133.1, 133.0, 132.9, 132.34, 132.27, 132.25, 132.2, 132.13,132.10, 132.07, 132.0, 131.9, 130.33, 130.32, 130.27, 130.1, 129.5, 129.3,129.23, 129.18, 129.09, 129.08, 129.0, 128.7, 128.5, 128.11, 128.05, 128.04,127.91, 127.8, 127.74, 127.68, 127.6, 127.5, 126.6, 32.6, 32.2 (d, J = 9.4Hz), 21.4, 21.3, 11. (d, J = 3.6 Hz), 10.6; 31 31P NMR (162 MHz, CDCl3) δ 30.18(s), -6.40 (s); HRMS (EI-TOF) m / z Calcd for C 42 18 38 36OP2Si [M] + : 648.2240, found:648.2244.

[0344] Example 28: I-28

[0345]

[0346] White solid 1 H NMR (400 MHz, CDCl3) δ 7.41 (t, J = 8.4 Hz, 2H), 7.34–7.16(m, 9H), 7.16–6.93 (m, 9H), 6.89–6.77 (m, 2H), 6.72 (t, J = 7.6 Hz, 2H), 3.78–3.39 (m, 2H), 3.28–3.00 (m, 2H), 2.31 (s, 3H), 2.13 (s, 3H), 1.51 (t, J= 11.2 Hz, 1H), 1.11–0.79 (m, 3H); 13 C NMR (100 MHz, CDCl3) δ 157.6, 157.4,155.4, 155.3, 147.6, 147.0, 142.0, 141.9, 141.82, 141.79, 141.0, 140.9,139.1, 139.0, 138.0, 137.9, 137.9, 137.8, 137.5, 137.4, 136.8, 134.8, 133.8,133.6, 133.4, 133.1, 133.0, 132.9, 132.34, 132.27, 132.25, 132.2, 132.13,132.10, 132.07, 132.0, 131.9, 130.33, 130.32, 130.27, 130.1, 129.5, 129.3,129.23, 129.18, 129.09, 129.08, 129.0, 128.7, 128.5, 128.11, 128.05, 128.04,127.91, 127.8, 127.74, 127.68, 127.6, 127.5, 126.6, 32.6, 32.2 (d, J = 9.4Hz), 21.4, 21.3, 11.1 (d, J = 3.6 Hz), 10.6; 31 P NMR (162 MHz, CDCl3) δ 30.18(s), -6.40 (s); HRMS (EI-TOF) m / z Calcd for C 42 H 38 OP2Si [M] +: 648.2240, found:648.2242.

[0347] Example 29: I-29

[0348]

[0349] White solid 1 H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8 Hz, 1H), 7.75–7.66 (m, 2H), 7.59 (ddd, J = 6.8 Hz, 2H), 7.54 (td, J = 2.0 Hz, 2H), 7.51(dt, J = 7.2, 1.2 Hz, 1H), 7.40–7.34 (m, 4H), 7.34–7.30 (m, 2H), 7.34–7.28(m, 3H), 7.24–7.16 (m, 3H), 7.15–7.09 (m, 4H), 3.00–2.85 (m, 6H), 1.46 (ddd,J = 7.8, 2.0 Hz, 4H), 1.27 (d, J = 6.8 Hz, 12H); 13 C NMR (100 MHz, CDCl3) δ153.9, 153.7, 151.6, 150.9, 143.6, 141.5, 138.0, 137.0, 134.0, 133.3, 131.5,130.0, 129.2, 129.0, 128.9, 128.39, 128.37, 128.07, 128.05, 128.0, 125.9,122.0, 33.6, 31.6, 31.3, 23.9, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.51 (s), -6.41 (s); HRMS (EI-TOF) m / z Calcd for C 46 H 46 OP2Si [M] + : 704.2793, found:704.2795.

[0350] Example 30: I-30

[0351]

[0352] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8 Hz, 1H), 7.75–7.66 (m, 2H), 7.59 (ddd, J = 6.8 Hz, 2H), 7.54 (td, J = 2.0 Hz, 2H), 7.51(dt, J = 7.2, 1.2 Hz, 1H), 7.40–7.34 (m, 4H), 7.34–7.30 (m, 2H), 7.34–7.28(m, 3H), 7.24–7.16 (m, 3H), 7.15–7.09 (m, 4H), 3.00–2.85 (m, 6H), 1.46 (ddd,J = 7.8, 2.0 Hz, 4H), 1.27 (d, J = 6.8 Hz, 12H); 13 C NMR (100 MHz, CDCl3) δ153.9, 153.7, 151.6, 150.9, 143.6, 141.5, 138.0, 137.0, 134.0, 133.3, 131.5,130.0, 129.2, 129.0, 128.9, 128.39, 128.37, 128.07, 128.05, 128.0, 125.9,122.0, 33.6, 31.6, 31.3, 23.9, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.51 (s), -6.41 (s); HRMS (EI-TOF) m / z Calcd for C 46 H 46 OP2Si [M] + : 704.2793, found:704.2796.

[0353] Example 31: I-31

[0354]

[0355] White solid 1 H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H),7.75–7.66 (m, 4H), 7.64 (dt, J = 5.6, 2.0 Hz, 2H), 7.51 (dq, J = 7.2, 1.2 Hz,1H), 7.41–7.28 (m, 11H), 7.23–7.16 (m, 1H), 7.15–7.09 (m, 4H), 2.96 (dddd, J= 8.6, 5.7, 4.5, 2.0 Hz, 4H), 1.46 (dddd, J = 7.8, 2.0 Hz, 4H), 1.34 (s, 18H); 13 C NMR (100 MHz, CDCl3) δ 153.9, 153.7, 152.9, 151.6, 143.6, 141.5, 138.0,137.0, 134.0, 132.9, 132.0, 130.0, 129.0, 128.9, 128.4, 128.2, 128.07,128.05, 128.0, 125.9, 122.0, 34.6, 31.6, 31.30, 31.25, 14.7; 31 P NMR (162 MHz, CDCl3) δ 29.89 (s), -6.49 (s); HRMS (EI-TOF) m / z Calcd for C 48 H 50 OP2Si [M] + :732.3106, found: 732.3110.

[0356] Example 32: I-32

[0357]

[0358] White solid 1 H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H),7.75–7.66 (m, 4H), 7.64 (dt, J = 5.6, 2.0 Hz, 2H), 7.51 (dq, J = 7.2, 1.2 Hz,1H), 7.41–7.28 (m, 11H), 7.23–7.16 (m, 1H), 7.15–7.09 (m, 4H), 2.96 (dddd, J= 8.6, 5.7, 4.5, 2.0 Hz, 4H), 1.46 (dddd, J = 7.8, 2.0 Hz, 4H), 1.34 (s, 18H); 13 C NMR (100 MHz, CDCl3) δ 153.9, 153.7, 152.9, 151.6, 143.6, 141.5, 138.0,137.0, 134.0, 132.9, 132.0, 130.0, 129.0, 128.9, 128.4, 128.2, 128.07,128.05, 128.0, 125.9, 122.0, 34.6, 31.6, 31.30, 31.25, 14.7; 31 P NMR (162 MHz, CDCl3) δ 29.89 (s), -6.49 (s); HRMS (EI-TOF) m / z Calcd for C 48 H 50 OP2Si [M] + :732.3106, found: 732.3111.

[0359] Example 33: I-33

[0360]

[0361] White solid 1H NMR (400 MHz, CDCl3) δ 8.07–7.99 (m, 3H), 7.76–7.65 (m,6H), 7.59 (dd, J = 10.0, 6.8 Hz, 2H), 7.51 (dq, J = 7.6, 1.2 Hz, 1H), 7.41–7.30 (m, 4H), 7.34–7.28 (m, 3H), 7.23–7.16 (m, 1H), 7.15–7.09 (m, 4H), 2.96 (dddd, J = 8.4, 2.0 Hz, 4H), 1.46 (dddd, J = 7.8, 2.0 Hz, 4H).; 13 C NMR (100MHz, CDCl3) δ 153.9, 153.7, 151.6, 143.6, 141.3, 137.8, 137.0, 134.0, 133.7,133.2, 132.0, 130.0, 129.2, 128.9, 128.7, 128.4, 128.3, 128.07, 128.05,128.0, 125.9, 123.9, 122.0, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 31.15 (s), -6.52 (s); 19 F NMR (375 MHz, CDCl3) δ -63.37; HRMS (EI-TOF) m / z Calcd forC 42 H 32 F6OP2Si [M] + : 756.1602, found: 756.1600.

[0362] Example 34: I-34

[0363]

[0364] White solid 1H NMR (400 MHz, CDCl3) δ 8.07–7.99 (m, 3H), 7.76–7.65 (m,6H), 7.59 (dd, J = 10.0, 6.8 Hz, 2H), 7.51 (dq, J = 7.6, 1.2 Hz, 1H), 7.41–7.30 (m, 4H), 7.34–7.28 (m, 3H), 7.23–7.16 (m, 1H), 7.15–7.09 (m, 4H), 2.96 (dddd, J = 8.4, 2.0 Hz, 4H), 1.46 (dddd, J = 7.8, 2.0 Hz, 4H).; 13 C NMR (100MHz, CDCl3) δ 153.9, 153.7, 151.6, 143.6, 141.3, 137.8, 137.0, 134.0, 133.7,133.2, 132.0, 130.0, 129.2, 128.9, 128.7, 128.4, 128.3, 128.07, 128.05,128.0, 125.9, 123.9, 122.0, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 31.15 (s), -6.52 (s); 19 F NMR (375 MHz, CDCl3) δ -63.37; HRMS (EI-TOF) m / z Calcd forC 42 H 32 F6OP2Si [M] + : 756.1602, found: 756.1601.

[0365] Example 35: I-35

[0366]

[0367] White solid 11H NMR (400 MHz, CDCl3) δ 7.46 (d, J = 7.6 Hz, 1H), 7.38–7.22(m, 6H), 7.22–7.06 (m, 7H), 7.06–6.92 (m, 4H), 6.84 (d, J = 15.2 Hz, 5H),6.61 (dd, J = 11.6, 7.6 Hz, 1H), 3.77 (s, 3H), 3.70–3.44 (m, 5H), 3.28–3.04(m, 2H), 1.60–1.45 (m, 1H), 1.17–0.74 (m, 3H); 13 13C NMR (100 MHz, CDCl3) δ159.4, 159.3, 158.9, 158.8, 157.7, 157.6, 155.2, 155.0, 147.6, 147.1, 141.9,141.8, 141.0, 140.9, 139.2, 139.0, 137.8, 137.7, 137.4, 136.3, 136.0, 135.0,134.5, 133.7, 133.50, 133.48, 133.0, 132.8, 130.40, 130.38, 130.2, 129.49,129.46, 129.4, 129.3, 129.1, 128.9, 128.7, 128.6, 128.1, 128.1, 127.9,127.83, 127.82, 127.8, 126.6, 124.5, 124.4, 124.3, 124.2, 117.63, 117.60,117.22, 117.19, 116.8, 116.7, 116.5, 116.4, 55.3, 55.1, 32.5, 32.3 (d, J =9.7 Hz), 11.1 (d, J = 3.7 Hz), 10.5; 31 31P NMR (162 MHz, CDCl3) δ 30.47 (s), -6.28 (s); HRMS (EI-TOF) m / z Calcd for C 42 17 38 24H38O3P2Si [M]+ + : 680.2138 found:680.2147.

[0368] Example 36: I-36

[0369]

[0370] White solid 1 H NMR (400 MHz, CDCl3) δ 7.46 (d, J = 7.6 Hz, 1H), 7.38–7.22(m, 6H), 7.22–7.06 (m, 7H), 7.06–6.92 (m, 4H), 6.84 (d, J = 15.2 Hz, 5H),6.61 (dd, J = 11.6, 7.6 Hz, 1H), 3.77 (s, 3H), 3.70–3.44 (m, 5H), 3.28–3.04(m, 2H), 1.60–1.45 (m, 1H), 1.17–0.74 (m, 3H); 13 C NMR (100 MHz, CDCl3) δ159.4, 159.3, 158.9, 158.8, 157.7, 157.6, 155.2, 155.0, 147.6, 147.1, 141.9,141.8, 141.0, 140.9, 139.2, 139.0, 137.8, 137.7, 137.4, 136.3, 136.0, 135.0,134.5, 133.7, 133.50, 133.48, 133.0, 132.8, 130.40, 130.38, 130.2, 129.49,129.46, 129.4, 129.3, 129.1, 128.9, 128.7, 128.6, 128.1, 128.1, 127.9,127.83, 127.82, 127.8, 126.6, 124.5, 124.4, 124.3, 124.2, 117.63, 117.60,117.22, 117.19, 116.8, 116.7, 116.5, 116.4, 55.3, 55.1, 32.5, 32.3 (d, J =9.7 Hz), 11.1 (d, J = 3.7 Hz), 10.5; 31 P NMR (162 MHz, CDCl3) δ 30.47 (s), -6.28 (s); HRMS (EI-TOF) m / z Calcd for C 42 H 38 O3P2Si [M] + : 680.2138 found:680.2146.

[0371] Example 37: I-37

[0372]

[0373] White solid 1 H NMR (400 MHz, CDCl3) δ 7.44 (d, J = 7.6 Hz, 1H), 7.32–7.21(m, 6H), 7.19 (d, J = 7.2 Hz, 1H), 7.17–7.04 (m, 6H), 6.81 (dd, J = 19.6, 12Hz, 4H), 6.87–6.74 (m, 5H), 6.54 (dd, J = 11.6, 7.6 Hz, 1H), 4.56–4.43 (m,1H), 4.37–4.23 (m, 1H), 3.69–3.50 (m, 2H), 3.27–3.01 (m, 2H), 1.50–1.38 (m,1H), 1.27 (t, J = 6.0 Hz, 6H), 1.19 (dd, J = 6.0, 3.2 Hz, 6H), 1.15–1.04 (m,1H), 1.04–0.81 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 157.7, 157.6, 157.5, 157.4,157.3, 157.1, 155.1, 154.9, 147.9, 147.3, 141.9, 141.9, 141.79, 141.76,141.0, 140.9, 139.1, 138.9, 137.8, 137.7, 137.4, 136.3, 135.9, 134.9, 134.6,133.6, 133.5, 133.4, 133.0, 132.9, 130.4, 130.3, 130.2, 129.4, 129.39,129.35, 129.3, 129.1, 129.0, 128.7, 128.5, 128.12, 128.06, 127.9, 127.82,127.80, 127.79, 126.6, 124.3, 124.2, 124.0, 123.9, 119.59, 119.56, 118.93,118.90, 118.7, 118.6, 118.2, 118.1, 69.9, 69.7, 32.5, 32.3 (d, J = 9.6 Hz),21.89, 21.88, 21.80, 21.79, 11.3 (d, J = 3.6 Hz), 10.5; 31 P NMR (162 MHz, CDCl3) δ 30.59 (s), -6.24 (s); HRMS (EI-TOF) m / z Calcd for C 46 H 46 O3P2Si [M] + 736.2764 found: 736.2767.

[0374] Example 38: I-38

[0375]

[0376] White solid 1H NMR (400 MHz, CDCl3) δ 7.44 (d, J = 7.6 Hz, 1H), 7.32–7.21(m, 6H), 7.19 (d, J = 7.2 Hz, 1H), 7.17–7.04 (m, 6H), 6.81 (dd, J = 19.6, 12Hz, 4H), 6.87–6.74 (m, 5H), 6.54 (dd, J = 11.6, 7.6 Hz, 1H), 4.56–4.43 (m,1H), 4.37–4.23 (m, 1H), 3.69–3.50 (m, 2H), 3.27–3.01 (m, 2H), 1.50–1.38 (m,1H), 1.27 (t, J = 6.0 Hz, 6H), 1.19 (dd, J = 6.0, 3.2 Hz, 6H), 1.15–1.04 (m,1H), 1.04–0.81 (m, 2H); 13 C NMR (100 MHz, CDCl3) δ 157.7, 157.6, 157.5, 157.4,157.3, 157.1, 155.1, 154.9, 147.9, 147.3, 141.9, 141.9, 141.79, 141.76,141.0, 140.9, 139.1, 138.9, 137.8, 137.7, 137.4, 136.3, 135.9, 134.9, 134.6,133.6, 133.5, 133.4, 133.0, 132.9, 130.4, 130.3, 130.2, 129.4, 129.39,129.35, 129.3, 129.1, 129.0, 128.7, 128.5, 128.12, 128.06, 127.9, 127.82,127.80, 127.79, 126.6, 124.3, 124.2, 124.0, 123.9, 119.59, 119.56, 118.93,118.90, 118.7, 118.6, 118.2, 118.1, 69.9, 69.7, 32.5, 32.3 (d, J = 9.6 Hz),21.89, 21.88, 21.80, 21.79, 11.3 (d, J = 3.6 Hz), 10.5; 31P NMR (162 MHz, CDCl3) δ 30.59 (s), -6.24 (s); HRMS (EI-TOF) m / z Calcd for C 46 H 46 O3P2Si [M] + 736.2764 found: 736.2768.

[0377] Example 39: I-39

[0378]

[0379] White solid 1 H NMR (400 MHz, CDCl3) δ 7.44 (d, J = 7.6 Hz, 1H), 7.39–7.21(m, 16H), 7.21–6.92 (m, 11H), 6.90 (d, J = 6.0 Hz, 1H), 6.87–6.71 (m, 4H), 6.61 (dd, J = 11.6, 7.6 Hz, 1H), 4.99 (s, 2H), 4.79 (d, J = 2.8 Hz, 2H), 3.70–3.45 (m, 2H), 3.28–3.00 (m, 2H), 1.52–1.40 (m, 1H), 1.11–1.02 (m, 1H),1.02–0.82 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 158.5, 158.3, 158.1, 158.0,157.6, 157.5, 155.3, 155.1, 147.8, 147.2, 142.01, 141.98, 141.9, 141.8,141.0, 140.9, 139.1, 139.0, 137.8, 137.7, 137.2, 136.5, 136.4, 136.1, 136.0,135.0, 134.6, 133.6, 133.4, 133.0, 132.9, 130.4, 130.3, 130.1, 129.6, 129.5, 129.4, 129.2, 129.0, 128.7, 128.6, 128.54, 128.49, 128.14, 128.08, 128.01, 127.96, 127.9, 127.84, 127.80, 127.6, 127.5, 126.6, 124.7, 124.6, 124.5, 124.4, 118.7, 118.6, 118.22, 118.20, 117.5, 117.42, 117.39, 117.3, 70.0, 69.8, 32.6, 32.3 (d, J = 9.6 Hz), 11.2 (d, J = 4.0 Hz), 10.6; 31 P NMR (162MHz, CDCl3) δ 30.21 (s), -6.31 (s); HRMS (EI-TOF) m / z Calcd for C 54 H 46 O3P2Si[M] + Found: 832.2764.

[0380] Example 40: I-40

[0381]

[0382] White solid 1H NMR (400 MHz, CDCl3) δ 7.44 (d, J = 7.6 Hz, 1H), 7.39–7.21(m, 16H), 7.21–6.92 (m, 11H), 6.90 (d, J = 6.0 Hz, 1H), 6.87–6.71 (m, 4H),6.61 (dd, J = 11.6, 7.6 Hz, 1H), 4.99 (s, 2H), 4.79 (d, J = 2.8 Hz, 2H),3.70–3.45 (m, 2H), 3.28–3.00 (m, 2H), 1.52–1.40 (m, 1H), 1.11–1.02 (m, 1H),1.02–0.82 (m, 2H); 13 C NMR (100 MHz, CDCl3) δ 158.5, 158.3, 158.1, 158.0,157.6, 157.5, 155.3, 155.1, 147.8, 147.2, 142.01, 141.98, 141.9, 141.8,141.0, 140.9, 139.1, 139.0, 137.8, 137.7, 137.2, 136.5, 136.4, 136.1, 136.0,135.0, 134.6, 133.6, 133.4, 133.0, 132.9, 130.4, 130.3, 130.1, 129.6, 129.5,129.4, 129.2, 129.0, 128.7, 128.6, 128.54, 128.49, 128.14, 128.08, 128.01,127.96, 127.9, 127.84, 127.80, 127.6, 127.5, 126.6, 124.7, 124.6, 124.5,124.4, 118.7, 118.6, 118.22, 118.20, 117.5, 117.42, 117.39, 117.3, 70.0,69.8, 32.6, 32.3 (d, J = 9.6 Hz), 11.2 (d, J = 4.0 Hz), 10.6; 31 P NMR (162MHz, CDCl3) δ 30.21 (s), -6.31 (s); HRMS (EI-TOF) m / z Calcd for C 54 H 46 O3P2Si[M] +832.2764 found: 832.2765.

[0383] Example 41: I-41

[0384]

[0385] White solid 1 H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.1 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2t Hz, 1H), 7.59 (dd, J = 2.4,1.2 Hz, 1H), 7.58 (dd, J = 2.4, 1.2 Hz, 1H), 7.54–7.48 (m, 3H), 7.40–7.35 (m,4H), 7.35–7.28 (m, 5H), 7.26 (ddd, J = 6.8, 2.4, 1.2 Hz, 2H), 7.23–7.16 (m,1H), 7.15–7.09 (m, 4H), 3.00–2.92 (m, 4H), 1.49–1.43 (m, 4H); 13 C NMR (100MHz, CDCl3) δ 154.0, 153.7, 152.3, 151.6, 143.6, 141.2, 138.0, 137.0, 134.4,134.0, 130.0, 129.7, 128.9, 128.4, 128.07, 128.05, 128.0, 126.0, 125.9,125.2, 122.0, 121.5, 120.4, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 29.52 (s), -6.48 (s); 19 F NMR (375 MHz, CDCl3) δ -58.13; HRMS (EI-TOF) m / z Calcd forC 42 H 32 F6O3P2Si [M] + 788.1500 found: 788.1503.

[0386] Example 42: I-42

[0387]

[0388] White solid 1 H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.1 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2t Hz, 1H), 7.59 (dd, J = 2.4,1.2 Hz, 1H), 7.58 (dd, J = 2.4, 1.2 Hz, 1H), 7.54–7.48 (m, 3H), 7.40–7.35 (m,4H), 7.35–7.28 (m, 5H), 7.26 (ddd, J = 6.8, 2.4, 1.2 Hz, 2H), 7.23–7.16 (m,1H), 7.15–7.09 (m, 4H), 3.00–2.92 (m, 4H), 1.49–1.43 (m, 4H); 13 C NMR (100MHz, CDCl3) δ 154.0, 153.7, 152.3, 151.6, 143.6, 141.2, 138.0, 137.0, 134.4,134.0, 130.0, 129.7, 128.9, 128.4, 128.07, 128.05, 128.0, 126.0, 125.9,125.2, 122.0, 121.5, 120.4, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 29.52 (s), -6.48 (s); 19 F NMR (375 MHz, CDCl3) δ -58.13; HRMS (EI-TOF) m / z Calcd forC 42 H 32 F6O3P2Si [M] + 788.1500 found: 788.1504.

[0389] Example 43: I-43

[0390]

[0391] White solid 11H NMR (400 MHz, CDCl3) δ 7.45 (d, J = 7.6 Hz, 1H), 7.37–7.20(m, 6H), 7.20–7.08 (m, 7H), 7.08–6.97 (m, 3H), 6.90–6.75 (m, 3H), 6.63 (t, J= 7.2 Hz, 2H), 3.81–3.69 (m, 1H), 3.54–3.41 (m, 1H), 3.27–3.03 (m, 2H), 2.29(s, 6H), 2.14 (s, 6H), 1.60–1.49 (m, 1H), 1.09–0.82 (m, 3H); 13 13C NMR (100 MHz,CDCl3) δ 157.4, 157.2, 155.7, 155.5, 147.5, 147.0, 141.88, 141.86, 141.74,141.71, 141.0, 140.9, 138.8, 138.7, 138.2, 138.10, 138.07, 137.7, 137.6,137.3, 137.2, 137.0, 135.1, 134.1, 133.3, 133.2, 133.1, 133.02, 132.98,132.0, 130.23, 130.17, 130.01, 129.59, 129.6, 129.49, 129.47, 129.45, 129.08,129.05, 128.7, 128.5, 128.14, 128.08, 127.9, 127.63, 127.57, 127.5, 126.6,32.7, 32.1 (d, J = 8.4 Hz), 21.3, 21.2, 11.0 (d, J = 3.6 Hz), 10.8; 31 31P NMR(162 MHz, CDCl3) δ 29.94 (s), -6.51 (s); HRMS (EI-TOF) m / z Calcd forC 44 H 42 OP2Si [M] + : 676.2553 found: 676.2560.

[0392] Example 44: I-44

[0393]

[0394] White solid 1 H NMR (400 MHz, CDCl3) δ 7.45 (d, J = 7.6 Hz, 1H), 7.37–7.20(m, 6H), 7.20–7.08 (m, 7H), 7.08–6.97 (m, 3H), 6.90–6.75 (m, 3H), 6.63 (t, J= 7.2 Hz, 2H), 3.81–3.69 (m, 1H), 3.54–3.41 (m, 1H), 3.27–3.03 (m, 2H), 2.29(s, 6H), 2.14 (s, 6H), 1.60–1.49 (m, 1H), 1.09–0.82 (m, 3H); 13 C NMR (100 MHz, CDCl3) δ 157.4, 157.2, 155.7, 155.5, 147.5, 147.0, 141.88, 141.86, 141.74,141.71, 141.0, 140.9, 138.8, 138.7, 138.2, 138.10, 138.07, 137.7, 137.6,137.3, 137.2, 137.0, 135.1, 134.1, 133.3, 133.2, 133.1, 133.02, 132.98,132.0, 130.23, 130.17, 130.01, 129.59, 129.6, 129.49, 129.47, 129.45, 129.08,129.05, 128.7, 128.5, 128.14, 128.08, 127.9, 127.63, 127.57, 127.5, 126.6,32.7, 32.1 (d, J = 8.4 Hz), 21.3, 21.2, 11.0 (d, J = 3.6 Hz), 10.8; 31 P NMR(162 MHz, CDCl3) δ 29.94 (s), -6.51 (s); HRMS (EI-TOF) m / z Calcd forC 44 H 42 OP2Si [M] + Found: 676.2553; Found: 676.2561.

[0395] Example 45: I-45

[0396]

[0397] White solid 1 H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.51 (dq, J = 7.2,1.2 Hz, 1H), 7.46 (d, J = 2.4 Hz, 4H), 7.40–7.34 (m, 2H), 7.34–7.27 (m, 5H), 7.23–7.16 (m, 3H), 7.15–7.09 (m, 4H), 3.25–2.66 (m, 4H), 1.61–1.38 (m, 4H),1.24 (d, J = 6.4 Hz, 12H); 13 C NMR (100 MHz, CDCl3) δ 153.9, 153.7, 151.6,151.5, 143.6, 140.8, 138.0, 137.0, 134.0, 132.2, 130.0, 128.9, 128.4, 128.07,128.05, 128.0, 127.4, 126.8, 125.9, 122.0, 34.6, 31.6, 31.3, 23.7, 14.7; 31 PNMR (162 MHz, CDCl3) δ 30.04 (s), -6.52 (s); HRMS (EI-TOF) m / z Calcd forC 52 H 58 OP2Si [M] + 788.3732 found: 788.3730.

[0398] Example 46: I-46

[0399]

[0400] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.51 (dq, J = 7.2,1.2 Hz, 1H), 7.46 (d, J = 2.4 Hz, 4H), 7.40–7.34 (m, 2H), 7.34–7.27 (m, 5H), 7.23–7.16 (m, 3H), 7.15–7.09 (m, 4H), 3.25–2.66 (m, 4H), 1.61–1.38 (m, 4H),1.24 (d, J = 6.4 Hz, 12H); 13 C NMR (100 MHz, CDCl3) δ 153.9, 153.7, 151.6,151.5, 143.6, 140.8, 138.0, 137.0, 134.0, 132.2, 130.0, 128.9, 128.4, 128.07,128.05, 128.0, 127.4, 126.8, 125.9, 122.0, 34.6, 31.6, 31.3, 23.7, 14.7; 31 PNMR (162 MHz, CDCl3) δ 30.04 (s), -6.52 (s); HRMS (EI-TOF) m / z Calcd forC 52 H 58 OP2Si [M] + 788.3732 found: 788.3732.

[0401] Example 47: I-47

[0402]

[0403] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.63 (d, J = 2.0Hz, 4H), 7.51 (dq, J = 7.2, 1.2 Hz, 1H), 7.40–7.34 (m, 1H), 7.34–7.28 (m,7H), 7.23–7.16 (m, 1H), 7.15–7.09 (m, 4H), 3.00–2.92 (m, 4H), 1.49–1.43 (m,4H), 1.36 (s, 18H); 13 C NMR (100 MHz, CDCl3) δ 153.2, 137.0, 134.0, 133.4,130.0, 128.9, 128.4, 128.07, 128.05, 128.0, 127.4, 125.9, 125.3, 122.0, 35.0,31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 31.03 (s), -6.49 (s); HRMS (EI-TOF) m / z Calcd for C 56 H 66 OP2Si [M] + 844.4358 found: 844.4359.

[0404] Example 48: I-48

[0405]

[0406] White solid 11H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.63 (d, J = 2.0 Hz, 4H), 7.51 (dq, J = 7.2, 1.2 Hz, 1H), 7.40–7.34 (m, 1H), 7.34–7.28 (m, 7H), 7.23–7.16 (m, 1H), 7.15–7.09 (m, 4H), 3.00–2.92 (m, 4H), 1.49–1.43 (m, 4H), 1.36 (s, 18H); 13 13C NMR (100 MHz, CDCl3) δ 153.2, 137.0, 134.0, 133.4, 130.0, 128.9, 128.4, 128.07, 128.05, 128.0, 127.4, 125.9, 125.3, 122.0, 35.0, 31.6, 31.3, 14.7; 31 31P NMR (162 MHz, CDCl3) δ 31.03 (s), -6.49 (s); HRMS (EI-TOF) m / z Calcd for C 56 18 66 31OP2Si [M] + : 844.4358 found: 844.4360.

[0407] Example 49: I-49

[0408]

[0409] White solid, 1 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.91 (d, J = 2.4 Hz, 4H), 7.84 (t, J = 2.4 Hz, 2H), 7.75–7.66 (m, 2H), 7.51 (dq, J = 7.2, 1.2 Hz, 1H), 7.41–7.28 (m, 7H), 7.23–7.16 (m, 1H), 7.15–7.09 (m, 4H), 3.00–2.92 (m, 4H), 1.49–1.43 (m, 4H);13 C NMR (100 MHz, CDCl3) δ153.9, 153.7, 151.6, 143.6, 141.04, 137.9, 137.0, 134.8, 134.04, 133.99,130.0, 128.9, 128.4, 128.07, 128.05, 128.03, 127.97, 126.2, 125.9, 123.6,122.0, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 29.59 (s), -6.50 (s); 19 FNMR (375 MHz, CDCl3) δ -63.40; HRMS (EI-TOF) m / z Calcd for C 44 H 30 F 12 OP2Si [M] + 892.1350 found: 892.1353.

[0410] Example 50: I-50

[0411]

[0412] White solid 1 H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.91 (d, J = 2.4 Hz, 4H), 7.84 (t, J = 2.4 Hz, 2H), 7.75–7.66 (m, 2H), 7.51(dq, J = 7.2, 1.2 Hz, 1H), 7.41–7.28 (m, 7H), 7.23–7.16 (m, 1H), 7.15–7.09 (m, 4H), 3.00–2.92 (m, 4H), 1.49–1.43 (m, 4H); 13C NMR (100 MHz, CDCl3) δ153.9, 153.7, 151.6, 143.6, 141.04, 137.9, 137.0, 134.8, 134.04, 133.99,130.0, 128.9, 128.4, 128.07, 128.05, 128.03, 127.97, 126.2, 125.9, 123.6,122.0, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 29.59 (s), -6.50 (s); 19 FNMR (375 MHz, CDCl3) δ -63.40; HRMS (EI-TOF) m / z Calcd for C 44 H 30 F 12 OP2Si [M] + 892.1350 found: 892.1355.

[0413] Example 51: I-51

[0414]

[0415] White solid 1 H NMR (400 MHz, CDCl3) δ 7.44 (d, J = 7.6 Hz, 1H), 7.32–7.21(m, 5H), 7.22–7.03 (m, 7H), 6.85–6.74 (m, 3H), 6.69 (dd, J = 12.8, 2.0 Hz,2H), 6.55 (s, 1H), 6.47 (dd, J = 12.8, 2.4 Hz, 2H), 6.39 (s, 1H), 3.79–3.61(m, 7H), 3.60–3.42 (m, 7H), 3.18–3.07 (m, 2H), 1.56–1.45 (m, 1H), 0.98–0.86 (m, 3H); 13C NMR (100 MHz, CDCl3) δ 160.6, 160.4, 160.2, 160.0, 157.6, 157.5,155.3, 155.1, 147.3, 146.8, 141.8, 141.7, 141.61, 141.58, 141.0 140.9, 138.9,138.8, 138.0, 137.9, 136.9, 136.8, 135.8, 134.9, 133.9, 133.4, 133.24,133.19, 133.0, 130.4, 130.2, 130.2, 129.51, 129.48, 129.4, 128.7, 128.6,128.14, 128.08, 127.9, 127.73, 127.70, 127.67, 126.5, 109.8, 109.7, 109.6,109.5, 103.49, 103.47, 103.4, 103.3, 55.4, 55.2, 32.6, 32.1 (d, J = 8.8 Hz), 10.9 (d, J = 3.4 Hz), 10.6; 31 P NMR (162 MHz, CDCl3) δ 31.11 (s), -6.29 (s); HRMS (EI-TOF) m / z Calcd for C 44 H 42 O5P2Si [M] + 740.2350 found: 740.2354.

[0416] Example 52: I-52

[0417]

[0418] White solid 11H NMR (400 MHz, CDCl3) δ 7.44 (d, J = 7.6 Hz, 1H), 7.32–7.21(m, 5H), 7.22–7.03 (m, 7H), 6.85–6.74 (m, 3H), 6.69 (dd, J = 12.8, 2.0 Hz,2H), 6.55 (s, 1H), 6.47 (dd, J = 12.8, 2.4 Hz, 2H), 6.39 (s, 1H), 3.79–3.61(m, 7H), 3.60–3.42 (m, 7H), 3.18–3.07 (m, 2H), 1.56–1.45 (m, 1H), 0.98–0.86(m, 3H); 13 13C NMR (100 MHz, CDCl3) δ 160.6, 160.4, 160.2, 160.0, 157.6, 157.5,155.3, 155.1, 147.3, 146.8, 141.8, 141.7, 141.61, 141.58, 141.0 140.9, 138.9,138.8, 138.0, 137.9, 136.9, 136.8, 135.8, 134.9, 133.9, 133.4, 133.24,133.19, 133.0, 130.4, 130.2, 130.2, 129.51, 129.48, 129.4, 128.7, 128.6,128.14, 128.08, 127.9, 127.73, 127.70, 127.67, 126.5, 109.8, 109.7, 109.6,109.5, 103.49, 103.47, 103.4, 103.3, 55.4, 55.2, 32.6, 32.1 (d, J = 8.8 Hz),10.9 (d, J = 3.4 Hz), 10.6; 31 31P NMR (162 MHz, CDCl) δ 31.11 (s), -6.29 (s); HRMS (EI-TOF) m / z Calcd for C 44 19 42 18O5P2Si [M] + : 740.2350 found: 740.2352.

[0419] Example 53: I-53

[0420]

[0421] White solid, 1 H NMR (400 MHz, CDCl3) δ 7.42 (d, J = 7.6 Hz, 1H), 7.36–6.96(m, 14H), 6.85 (d, J = 12.0 Hz, 2H), 6.78 (dd, J = 7.6, 4.0 Hz, 1H), 6.66 (t,J = 7.2 Hz, 2H), 3.71 (s, 3H), 3.65 (s, 3H), 3.53–3.38 (m, 1H), 3.20–2.98 (m,2H), 2.23 (s, 6H), 2.06 (s, 6H), 1.62–1.48 (m, 1H), 1.02–0.82 (m, 3H); 13 C NMR(100 MHz, CDCl3) δ 159.59, 159.56, 159.5, 159.4, 157.4, 157.3, 155.6, 155.4,147.6, 147.04 141.9, 141.8, 141.70, 141.68, 141.0, 140.9, 139.0, 138.8,138.3, 138.2, 138.1, 137.2, 133.3, 133.2, 133.1, 133.0, 132.67, 132.65,132.57, 132.55, 130.9, 130.8, 130.5, 130.4, 130.24, 130.23, 130.2, 130.0,129.4, 129.2, 129.08, 129.05, 128.6, 128.5, 128.2, 128.13, 128.07, 127.9,127.8, 127.7, 127.6, 127.2, 126.5, 59.6, 59.4, 32.6, 32.1 (d, J = 8.6 Hz),16.2, 16.1, 11.0 (d, J = 3.6 Hz), 10.9; 31 P NMR (162 MHz, CDCl3) δ 29.07 (s), -6.50 (s); HRMS (EI-TOF) m / z Calcd for C 46 H 46 O3P2Si [M] + : 736.2764 found:736.2755.

[0422] Example 54: I-54

[0423]

[0424] White solid 1 H NMR (400 MHz, CDCl3) δ 7.42 (d, J = 7.6 Hz, 1H), 7.36–6.96(m, 14H), 6.85 (d, J = 12.0 Hz, 2H), 6.78 (dd, J = 7.6, 4.0 Hz, 1H), 6.66 (t,J = 7.2 Hz, 2H), 3.71 (s, 3H), 3.65 (s, 3H), 3.53–3.38 (m, 1H), 3.20–2.98 (m,2H), 2.23 (s, 6H), 2.06 (s, 6H), 1.62–1.48 (m, 1H), 1.02–0.82 (m, 3H); 13 C NMR (100 MHz, CDCl3) δ 159.59, 159.56, 159.5, 159.4, 157.4, 157.3, 155.6, 155.4,147.6, 147.04 141.9, 141.8, 141.70, 141.68, 141.0, 140.9, 139.0, 138.8,138.3, 138.2, 138.1, 137.2, 133.3, 133.2, 133.1, 133.0, 132.67, 132.65,132.57, 132.55, 130.9, 130.8, 130.5, 130.4, 130.24, 130.23, 130.2, 130.0,129.4, 129.2, 129.08, 129.05, 128.6, 128.5, 128.2, 128.13, 128.07, 127.9,127.8, 127.7, 127.6, 127.2, 126.5, 59.6, 59.4, 32.6, 32.1 (d, J = 8.6 Hz), 16.2, 16.1, 11.0 (d, J = 3.6 Hz), 10.9; 31 P NMR (162 MHz, CDCl3) δ 29.07 (s),-6.50 (s); HRMS (EI-TOF) m / z Calcd for C 46 H46 O3P2Si [M] + 736.2764 found:736.2758.

[0425] Example 55: I-55

[0426]

[0427] White solid 1 H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.61 (s, 4H), 7.52–7.48 (m, 1H), 7.41–7.35 (m, 2H), 7.35–7.28 (m, 5H), 7.23–7.17 (m, 1H), 7.14–7.08 (m, 4H), 3.82 (s, 6H), 3.12–2.83 (m, 4H), 1.49–1.43 (m, 4H), 1.41 (s,36H); 13 C NMR (100 MHz, CDCl3) δ 158.1, 140.6, 137.0, 134.0, 130.0, 129.5,128.9, 128.4, 128.07, 128.05, 128.0, 127.6, 125.9, 122.0, 61.1, 35.0, 31.6,31.3, 30.5, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.07 (s), -6.49 (s); HRMS (EI-TOF) m / z Calcd for C 58 H 70 O3P2Si [M] + 904.4569 found: 904.4572.

[0428] Example 56: I-56

[0429]

[0430] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.61 (s, 4H), 7.52–7.48 (m, 1H), 7.41–7.35 (m, 2H), 7.35–7.28 (m, 5H), 7.23–7.17 (m, 1H), 7.14–7.08 (m, 4H), 3.82 (s, 6H), 3.12–2.83 (m, 4H), 1.49–1.43 (m, 4H), 1.41 (s,36H); 13 C NMR (100 MHz, CDCl3) δ 158.1, 140.6, 137.0, 134.0, 130.0, 129.5,128.9, 128.4, 128.07, 128.05, 128.0, 127.6, 125.9, 122.0, 61.1, 35.0, 31.6,31.3, 30.5, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.07 (s), -6.49 (s); HRMS (EI-TOF) m / z Calcd for C 58 H 70 O3P2Si [M] + 904.4569 found: 904.4573.

[0431] Example 57: I-57

[0432]

[0433] White solid 1H NMR (400 MHz, CDCl3) δ 7.44–7.33 (m, 3H), 7.33–7.17 (m,8H), 7.17–7.05 (m, 3H), 7.01 (t, J = 7.6 Hz, 2H), 6.94–6.79 (m, 3H), 6.79–6.68 (m, 2H), 6.56 (t, J = 7.2 Hz, 2H), 6.46 (t, J = 7.6 Hz, 1H), 3.87–3.73(m, 1H), 3.47 (s, 3H), 3.43 (s, 3H), 3.41–3.32 (m, 1H), 3.21–3.03 (m, 2H),1.85–1.74 (m, 1H), 1.02–0.74 (m, 3H); 13 C NMR (100 MHz, CDCl3) δ 161.47,161.45, 160.10, 160.07, 156.47, 156.33, 156.00, 155.85, 147.66, 147.14,140.95, 140.93, 140.90, 140.83, 140.81, 140.78, 139.10, 138.87, 138.73,138.30, 138.17, 137.97, 134.81, 134.74, 133.88, 133.80, 133.36, 133.21,133.17, 133.03, 132.90, 132.88, 132.58, 132.56, 130.47, 130.46, 129.85,129.68, 129.24, 128.40, 128.36, 128.11, 128.04, 127.89, 127.62, 127.55,127.45, 126.63, 123.41, 122.37, 121.95, 120.94, 120.84, 120.73, 120.15,120.03, 111.50, 111.44, 110.28, 110.22, 55.43, 55.02, 32.83, 31.93 (d, J =7.8 Hz), 11.50, 11.15 (d, J = 3.6 Hz); 31 P NMR (162 MHz, CDCl3) δ 26.16 (s), -6.61 (s); HRMS (EI-TOF) m / z Calcd for C 42H 38 O3P2Si [M] + : 648.2167 found: 648.2165.

[0434] Example 58: I-58

[0435]

[0436] White solid 1 H NMR (400 MHz, CDCl3) δ 7.44–7.33 (m, 3H), 7.33–7.17 (m,8H), 7.17–7.05 (m, 3H), 7.01 (t, J = 7.6 Hz, 2H), 6.94–6.79 (m, 3H), 6.79–6.68 (m, 2H), 6.56 (t, J = 7.2 Hz, 2H), 6.46 (t, J = 7.6 Hz, 1H), 3.87–3.73(m, 1H), 3.47 (s, 3H), 3.43 (s, 3H), 3.41–3.32 (m, 1H), 3.21–3.03 (m, 2H),1.85–1.74 (m, 1H), 1.02–0.74 (m, 3H); 13C NMR (100 MHz, CDCl3) δ 161.47,161.45, 160.10, 160.07, 156.47, 156.33, 156.00, 155.85, 147.66, 147.14,140.95, 140.93, 140.90, 140.83, 140.81, 140.78, 139.10, 138.87, 138.73,138.30, 138.17, 137.97, 134.81, 134.74, 133.88, 133.80, 133.36, 133.21,133.17, 133.03, 132.90, 132.88, 132.58, 132.56, 130.47, 130.46, 129.85, 129.68, 129.24, 128.40, 128.36, 128.11, 128.04, 127.89, 127.62, 127.55, 127.45, 126.63, 123.41, 122.37, 121.95, 120.94, 120.84, 120.73, 120.15, 120.03, 111.50, 111.44, 110.28, 110.22, 55.43, 55.02, 32.83, 31.93 (d, J =7.8 Hz), 11.50, 11.15 (d, J = 3.6 Hz); 31 P NMR (162 MHz, CDCl3) δ 26.16 (s), -6.61 (s); HRMS (EI-TOF) m / z Calcd for C 42 H 38 O3P2Si [M] + : 648.2167 found:648.2168.

[0437] Example 59: I-59

[0438]

[0439] White solid 1H NMR (400 MHz, CDCl3) δ 7.96 (dd, J = 6.8, 1.2 Hz, 1H),7.82 (td, J = 7.2, 1.6 Hz, 2H), 7.77–7.70 (m, 3H), 7.69 (t, J = 7.0 Hz, 1H),7.51 (dq, J = 7.2, 1.2 Hz, 1H), 7.41–7.26 (m, 11H), 7.23–7.16 (m, 1H), 7.15–7.09 (m, 4H), 3.35–3.24 (m, 2H), 3.00–2.92 (m, 2H), 1.49–1.43 (m, 4H), 1.27(d, J = 6.8 Hz, 12H); 13 C NMR (100 MHz, CDCl3) δ 154.0, 153.7, 151.6, 149.2,146.4, 143.6, 138.4, 137.0, 134.0, 132.9, 132.7, 132.0, 130.0, 128.9, 128.7,128.4, 128.07, 128.05, 128.0, 127.8, 125.9, 122.0, 31.6, 31.3, 29.6, 23.5,14.7; 31 P NMR (162 MHz, CDCl3) δ 27.11 (s), -6.59 (s); HRMS (EI-TOF) m / z Calcdfor C 46 H 46 OP2Si [M] + 704.2793 found: 704.2795.

[0440] Example 60: I-60

[0441]

[0442] White solid 1H NMR (400 MHz, CDCl3) δ 7.96 (dd, J = 6.8, 1.2 Hz, 1H),7.82 (td, J = 7.2, 1.6 Hz, 2H), 7.77–7.70 (m, 3H), 7.69 (t, J = 7.0 Hz, 1H),7.51 (dq, J = 7.2, 1.2 Hz, 1H), 7.41–7.26 (m, 11H), 7.23–7.16 (m, 1H), 7.15–7.09 (m, 4H), 3.35–3.24 (m, 2H), 3.00–2.92 (m, 2H), 1.49–1.43 (m, 4H), 1.27(d, J = 6.8 Hz, 12H); 13 C NMR (100 MHz, CDCl3) δ 154.0, 153.7, 151.6, 149.2,146.4, 143.6, 138.4, 137.0, 134.0, 132.9, 132.7, 132.0, 130.0, 128.9, 128.7,128.4, 128.07, 128.05, 128.0, 127.8, 125.9, 122.0, 31.6, 31.3, 29.6, 23.5,14.7; 31 P NMR (162 MHz, CDCl3) δ 27.11 (s), -6.59 (s); HRMS (EI-TOF) m / z Calcdfor C 46 H 46 OP2Si [M] + Found: 704.2793.

[0443] Example 61: I-61

[0444]

[0445] White solid 11H NMR (400 MHz, CDCl3) δ 8.00–7.93 (m, 5H), 7.75–7.66 (m, 4H), 7.61–7.53 (m, 2H), 7.53–7.48 (m, 1H), 7.40–7.34 (m, 2H), 7.34–7.27 (m, 5H), 7.24–7.16 (m, 1H), 7.15–7.09 (m, 4H), 3.11–2.68 (m, 4H), 1.65–0.82 (m, 4H); 13 13C NMR (100 MHz, CDCl3) δ 154.0, 153.7, 151.6, 146.4, 143.6, 138.2, 137.0, 134.2, 134.0, 133.0, 131.8, 131.3, 130.0, 128.9, 128.8, 128.7, 128.4, 128.07, 128.05, 127.9, 126.3, 125.9, 122.0, 31.6, 31.3, 14.7; 31 31P NMR (162MHz, CDCl3) δ 29.05 (s), -6.54 (s); 19 19F NMR (375 MHz, CDCl3) δ -63.17; HRMS(EI-TOF) m / z Calcd for C 42 H 32 F6OP2Si [M] + : 756.1602 found: 756.1605.

[0446] Example 62: I-62

[0447]

[0448] White solid, 1 1H NMR (400 MHz, CDCl3) δ 8.00–7.93 (m, 5H), 7.75–7.66 (m, 4H), 7.61–7.53 (m, 2H), 7.53–7.48 (m, 1H), 7.40–7.34 (m, 2H), 7.34–7.27 (m, 5H), 7.24–7.16 (m, 1H), 7.15–7.09 (m, 4H), 3.11–2.68 (m, 4H), 1.65–0.82 (m, 4H); 1313C NMR (100 MHz, CDCl3) δ 154.0, 153.7, 151.6, 146.4, 143.6, 138.2, 137.0, 134.2, 134.0, 133.0, 131.8, 131.3, 130.0, 128.9, 128.8, 128.7, 128.4, 128.07, 128.05, 127.9, 126.3, 125.9, 122.0, 31.6, 31.3, 14.7; 31 31P NMR (162 MHz, CDCl3) δ 29.05 (s), -6.54 (s); 19 19F NMR (375 MHz, CDCl3) δ -63.17; HRMS(EI-TOF) m / z Calcd for C 42 H 32 6FOP2Si [M] + : 756.1602 found: 756.1603.

[0449] Example 63: I-63

[0450]

[0451] White solid, 1 1H NMR (400 MHz, CDCl3) δ 7.96 (dd, J = 7.2, 1.2 Hz, 1H), 7.79 (dd, J = 7.2, 1.6 Hz, 2H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.65 (t, J = 7.2 Hz, 1H), 7.60 (td, J = 7.2, 1.2 Hz, 2H), 7.54–7.48 (m, 1H), 7.41–7.35 (m, 4H), 7.35–7.29 (m, 5H), 7.23–7.16 (m, 1H), 7.15–7.09 (m, 4H), 7.05 (dd, J = 7.6, 1.2 Hz, 2H), 3.78 (s, 6H), 3.00–2.92 (m, 4H), 1.67–1.16 (m, 4H); 13C NMR(100 MHz, CDCl3) δ 160.4, 154.3, 153.7, 151.6, 146.1, 143.7, 138.4, 137.0,134.0, 133.9, 132.9, 130.0, 128.9, 128.8, 128.4, 128.07, 128.05, 126.0,123.1, 122.8, 122.0, 113.1, 56.1, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ28.16 (s), -6.53 (s); HRMS (EI-TOF) m / z Calcd for C 42 H 38 O3P2Si [M] + 680.2065 found: 680.2065.

[0452] Example 64: I-64

[0453]

[0454] White solid 1 H NMR (400 MHz, CDCl3) δ 7.96 (dd, J = 7.2, 1.2 Hz, 1H), 7.79 (dd, J = 7.2, 1.6 Hz, 2H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.65 (t, J =7.2 Hz, 1H), 7.60 (td, J = 7.2, 1.2 Hz, 2H), 7.54–7.48 (m, 1H), 7.41–7.35 (m,4H), 7.35–7.29 (m, 5H), 7.23–7.16 (m, 1H), 7.15–7.09 (m, 4H), 7.05 (dd, J =7.6, 1.2 Hz, 2H), 3.78 (s, 6H), 3.00–2.92 (m, 4H), 1.67–1.16 (m, 4H); 13C NMR(100 MHz, CDCl3) δ 160.4, 154.3, 153.7, 151.6, 146.1, 143.7, 138.4, 137.0,134.0, 133.9, 132.9, 130.0, 128.9, 128.8, 128.4, 128.07, 128.05, 126.0,123.1, 122.8, 122.0, 113.1, 56.1, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ28.16 (s), -6.53 (s); HRMS (EI-TOF) m / z Calcd for C 42 H 38 O3P2Si [M] + 680.2065 found: 680.2067.

[0455] Example 65: I-65

[0456]

[0457] White solid 1 H NMR (400 MHz, CDCl3) δ 8.10 (d, J = 13.2 Hz, 1H), 7.93–7.76 (m, 3H), 7.76–7.67 (m, 2H), 7.60 (t, J = 9.2 Hz, 1H), 7.57–7.42 (m, 6H),7.38 (t, J = 7.6 Hz, 1H), 7.34–7.27 (m, 1H), 7.26–6.99 (m, 10H), 6.92 (t, J =7.2 Hz, 2H), 6.80–6.70 (m, 1H), 6.65 (t, J = 7.6 Hz, 2H), 3.80–3.45 (m, 2H),3.28–3.04 (m, 2H), 1.76–1.51 (m, 1H), 1.13–0.77 (m, 3H); 13C NMR (100 MHz, CDCl3) δ 157.8, 157.7, 155.3, 155.2, 147.3, 146.7, 142.3, 142.2, 142.10,142.07, 141.0, 140.9, 139.2, 139.1, 137.60, 137.58, 137.5, 136.5, 134.47,134.45, 134.38, 134.36, 133.7, 133.63, 133.59, 133.5, 133.4, 132.9, 132.8,132.4, 132.3, 132.2, 132.1, 131.1, 130.5, 130.4, 130.3, 129.6, 129.5, 129.4,129.3, 129.0, 128.9, 128.8, 128.7, 128.1, 128.03, 127.99, 127.9, 127.8,127.72, 127.66, 127.62, 127.57, 127.5, 127.2, 127.11, 127.07, 127.0, 126.6,126.5, 126.3, 32.5, 32.3 (d, J = 9.4 Hz), 11.1 (d, J = 3.6 Hz), 10.7; 31 P NMR(162 MHz, CDCl3) δ 30.33 (s), -6.28 (s); HRMS (EI-TOF) m / z Calcd forC 48 H 38 OP2Si [M] + 720.2240 found: 720.2239.

[0458] Example 66: I-66

[0459]

[0460] White solid 1H NMR (400 MHz, CDCl3) δ 8.10 (d, J = 13.2 Hz, 1H), 7.93–7.76 (m, 3H), 7.76–7.67 (m, 2H), 7.60 (t, J = 9.2 Hz, 1H), 7.57–7.42 (m, 6H),7.38 (t, J = 7.6 Hz, 1H), 7.34–7.27 (m, 1H), 7.26–6.99 (m, 10H), 6.92 (t, J =7.2 Hz, 2H), 6.80–6.70 (m, 1H), 6.65 (t, J = 7.6 Hz, 2H), 3.80–3.45 (m, 2H),3.28–3.04 (m, 2H), 1.76–1.51 (m, 1H), 1.13–0.77 (m, 3H); 13 C NMR (100 MHz,CDCl3) δ 157.8, 157.7, 155.3, 155.2, 147.3, 146.7, 142.3, 142.2, 142.10,142.07, 141.0, 140.9, 139.2, 139.1, 137.60, 137.58, 137.5, 136.5, 134.47,134.45, 134.38, 134.36, 133.7, 133.63, 133.59, 133.5, 133.4, 132.9, 132.8,132.4, 132.3, 132.2, 132.1, 131.1, 130.5, 130.4, 130.3, 129.6, 129.5, 129.4,129.3, 129.0, 128.9, 128.8, 128.7, 128.1, 128.03, 127.99, 127.9, 127.8,127.72, 127.66, 127.62, 127.57, 127.5, 127.2, 127.11, 127.07, 127.0, 126.6,126.5, 126.3, 32.5, 32.3 (d, J = 9.4 Hz), 11.1 (d, J = 3.6 Hz), 10.7; 31 P NMR(162 MHz, CDCl3) δ 30.33 (s), -6.28 (s); HRMS (EI-TOF) m / z Calcd forC 48 H 38OP2Si [M] + 720.2240 found: 720.2243.

[0461] Example 67: I-67

[0462]

[0463] White solid 1 H NMR (400 MHz, CDCl3) δ 7.45 (d, J = 8.0 Hz, 1H), 7.29 (td,J = 7.6, 3.2 Hz, 1H), 7.26–7.15 (m, 6H), 7.09 (dd, J = 14.8, 7.6 Hz, 4H),7.05–6.89 (m, 3H), 6.89–6.76 (m, 4H), 6.51 (dd, J = 11.6, 7.8 Hz, 2H), 6.41(dd, J = 8.0, 2.4 Hz, 1H), 5.96 (d, J = 2.8 Hz, 2H), 5.83 (d, J = 4.4 Hz, 2H), 3.70–3.47 (m, 2H), 3.28–3.00 (m, 2H), 1.61–1.50 (m, 1H), 1.16–1.04 (m,1H), 1.03–0.80 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 157.7, 157.6, 155.3, 155.1,150.30, 150.28, 150.00, 149.97, 147.7, 147.56, 147.55, 147.3, 147.1, 147.0,142.0, 141.9, 141.80, 141.77, 141.04, 140.96, 139.3, 139.2, 137.9, 137.5,137.4, 136.9, 133.9, 133.7, 132.8, 132.6, 130.3, 130.2, 129.44, 129.39,128.7, 128.6, 128.12, 128.08, 128.0, 127.9, 127.79, 127.77, 127.7, 127.4,127.2, 127.1, 126.7, 126.6, 126.4, 125.3, 111.5, 111.3, 108.4, 108.3, 108.0,107.9, 101.4, 101.1, 32.5, 32.3 (d, J = 10.1 Hz), 11.1 (d, J = 3.7 Hz), 10.4; 31 P NMR (162 MHz, CDCl3) δ 30.69 (s), -6.45 (s); HRMS (EI-TOF) m / z Calcd forC 42 H 34 O5P2Si [M] + 708.1724 found: 708.1720.

[0464] Example 68: I-68

[0465]

[0466] White solid 1H NMR (400 MHz, CDCl3) δ 7.45 (d, J = 8.0 Hz, 1H), 7.29 (td,J = 7.6, 3.2 Hz, 1H), 7.26–7.15 (m, 6H), 7.09 (dd, J = 14.8, 7.6 Hz, 4H),7.05–6.89 (m, 3H), 6.89–6.76 (m, 4H), 6.51 (dd, J = 11.6, 7.8 Hz, 2H), 6.41(dd, J = 8.0, 2.4 Hz, 1H), 5.96 (d, J = 2.8 Hz, 2H), 5.83 (d, J = 4.4 Hz,2H), 3.70–3.47 (m, 2H), 3.28–3.00 (m, 2H), 1.61-1.50 (m, 1H), 1.16–1.04 (m,1H), 1.03–0.80 (m, 2H); 13 C NMR (100 MHz, CDCl3) δ 157.7, 157.6, 155.3, 155.1,150.30, 150.28, 150.00, 149.97, 147.7, 147.56, 147.55, 147.3, 147.1, 147.0,142.0, 141.9, 141.80, 141.77, 141.04, 140.96, 139.3, 139.2, 137.9, 137.5,137.4, 136.9, 133.9, 133.7, 132.8, 132.6, 130.3, 130.2, 129.44, 129.39,128.7, 128.6, 128.12, 128.08, 128.0, 127.9, 127.79, 127.77, 127.7, 127.4,127.2, 127.1, 126.7, 126.6, 126.4, 125.3, 111.5, 111.3, 108.4, 108.3, 108.0,107.9, 101.4, 101.1, 32.5, 32.3 (d, J = 10.1 Hz), 11.1 (d, J = 3.7 Hz), 10.4; 31 P NMR (162 MHz, CDCl3) δ 30.69 (s), -6.45 (s); HRMS (EI-TOF) m / z Calcd forC 42 H34 O5P2Si [M] + 708.1724 found: 708.1725.

[0467] Example 69: I-69

[0468]

[0469] White solid 1 H NMR (400 MHz, CDCl3) δ 7.57 (ddd, J = 31.6, 16.4, 8.0 Hz,3H), 7.49 (d, J = 8.4 Hz, 1H), 7.46–7.30 (m, 6H), 7.30–7.22 (m, 5H), 7.18(ddd, J = 14.8, 7.6, 4.8 Hz, 2H), 7.09 (ddd, J = 12.8, 6.4, 2.4 Hz, 2H), 6.90(t, J = 7.4 Hz, 1H), 6.83–6.71 (m, 3H), 6.67–6.52 (m, 3H), 3.80–3.67 (m, 1H),3.57–3.44 (m, 1H), 3.27–3.16 (m, 2H), 1.90–1.78 (m, 1H), 1.13–0.99 (m, 3H); 13C NMR (100 MHz, CDCl3) δ 157.8, 157.7, 157.7, 157.7, 157.6, 155.7, 155.6,151.2, 149.9, 149.8, 148.5, 146.8, 146.2, 142.43, 142.41, 142.3, 142.2,141.42, 141.35, 138.9, 138.8, 137.4, 137.3, 134.0, 133.4, 133.2, 133.1,132.9, 132.8, 130.51, 130.48, 130.4, 129.9, 129.7, 129.6, 129.3, 129.2,128.2, 128.1, 127.9, 127.8, 127.71, 127.69, 126.74, 126.69, 126.64, 126.59,126.5, 123.4, 123.2, 122.5, 122.4, 119.4, 119.2, 119.0, 118.8, 112.2, 112.1,32.5, 32.2 (d, J = 8.4 Hz), 10.9 (d, J = 3.8 Hz), 10.8; 31 P NMR (162 MHz, CDCl3) δ 6.28 (s), -6.45 (s); HRMS (EI-TOF) m / z Calcd for C 44 H 34 O3P2Si [M] + 700.1825 found: 700.1833.

[0470] Example 70: I-70

[0471]

[0472] White solid 1H NMR (400 MHz, CDCl3) δ 7.57 (ddd, J = 31.6, 16.4, 8.0 Hz,3H), 7.49 (d, J = 8.4 Hz, 1H), 7.46–7.30 (m, 6H), 7.30–7.22 (m, 5H), 7.18(ddd, J = 14.8, 7.6, 4.8 Hz, 2H), 7.09 (ddd, J = 12.8, 6.4, 2.4 Hz, 2H), 6.90(t, J = 7.4 Hz, 1H), 6.83–6.71 (m, 3H), 6.67–6.52 (m, 3H), 3.80–3.67 (m, 1H),3.57–3.44 (m, 1H), 3.27–3.16 (m, 2H), 1.90–1.78 (m, 1H), 1.13–0.99 (m, 3H); 13 C NMR (100 MHz, CDCl3) δ 157.8, 157.7, 157.7, 157.7, 157.6, 155.7, 155.6,151.2, 149.9, 149.8, 148.5, 146.8, 146.2, 142.43, 142.41, 142.3, 142.2,141.42, 141.35, 138.9, 138.8, 137.4, 137.3, 134.0, 133.4, 133.2, 133.1,132.9, 132.8, 130.51, 130.48, 130.4, 129.9, 129.7, 129.6, 129.3, 129.2,128.2, 128.1, 127.9, 127.8, 127.71, 127.69, 126.74, 126.69, 126.64, 126.59,126.5, 123.4, 123.2, 122.5, 122.4, 119.4, 119.2, 119.0, 118.8, 112.2, 112.1,32.5, 32.2 (d, J = 8.4 Hz), 10.9 (d, J = 3.8 Hz), 10.8; 31 P NMR (162 MHz,CDCl3) δ 6.28 (s), -6.45 (s); HRMS (EI-TOF) m / z Calcd for C 44 H 34 O3P2Si [M] +700.1825 found: 700.1831.

[0473] Example 71: I-71

[0474]

[0475] White solid 1 H NMR (400 MHz, CDCl3) δ 7.43 (d, J = 5.6 Hz, 1H), 7.31–7.12(m, 7H), 7.11 (t, J = 7.2 Hz, 4H), 7.07–6.93 (m, 3H), 6.91–6.78 (m, 4H), 6.70(dd, J = 12.8, 2.0 Hz, 1H), 6.55–6.41 (m, 2H), 4.22 (dd, J = 13.2, 5.2 Hz, 4H), 4.14 (t, J = 4.0 Hz, 2H), 4.09–4.04 (m, 2H), 3.66–3.50 (m, 2H), 3.26–2.99 (m, 2H), 1.64–1.45 (m, 1H), 1.13–1.00 (m, 1H), 1.00–0.86 (m, 1H); 13C NMR(100 MHz, CDCl3) δ 157.6, 157.4, 155.3, 155.2, 147.7, 147.1, 146.3, 146.2,146.0, 145.9, 143.3, 143.1, 142.9, 142.7, 141.77, 141.75, 141.61, 141.60,140.94, 140.87, 139.3, 139.1, 138.1, 137.7, 137.6, 137.0, 133.8, 133.6,133.0, 132.8, 130.34, 130.28, 130.2, 129.4, 129.3, 129.2, 128.7, 128.5,128.1, 128.0, 127.90, 127.87, 127.81, 127.76, 127.2, 126.6, 126.1, 125.9,125.6, 125.5, 125.5, 125.4, 124.8, 121.2, 121.13, 121.09, 121.0, 117.4,117.3, 117.0, 116.9, 64.4, 64.3, 64.1, 63.8, 32.5, 32.3 (d, J = 10.0 Hz), 11.2 (d, J = 3.6 Hz), 10.5; 31 P NMR (162 MHz, CDCl3) δ 29.59 (s), -6.45 (s); HRMS (EI-TOF) m / z Calcd for C 44 H 38 O5P2Si [M] + 736.2037 found: 736.2029.

[0476] Example 72: I-72

[0477]

[0478] White solid 1H NMR (400 MHz, CDCl3) δ 7.43 (d, J = 5.6 Hz, 1H), 7.31–7.12(m, 7H), 7.11 (t, J = 7.2 Hz, 4H), 7.07–6.93 (m, 3H), 6.91–6.78 (m, 4H), 6.70(dd, J = 12.8, 2.0 Hz, 1H), 6.55–6.41 (m, 2H), 4.22 (dd, J = 13.2, 5.2 Hz,4H), 4.14 (t, J = 4.0 Hz, 2H), 4.09–4.04 (m, 2H), 3.66–3.50 (m, 2H), 3.26–2.99 (m, 2H), 1.64–1.45 (m, 1H), 1.13–1.00 (m, 1H), 1.00–0.86 (m, 1H); 13 C NMR(100 MHz, CDCl3) δ 157.6, 157.4, 155.3, 155.2, 147.7, 147.1, 146.3, 146.2,146.0, 145.9, 143.3, 143.1, 142.9, 142.7, 141.77, 141.75, 141.61, 141.60,140.94, 140.87, 139.3, 139.1, 138.1, 137.7, 137.6, 137.0, 133.8, 133.6,133.0, 132.8, 130.34, 130.28, 130.2, 129.4, 129.3, 129.2, 128.7, 128.5,128.1, 128.0, 127.90, 127.87, 127.81, 127.76, 127.2, 126.6, 126.1, 125.9,125.6, 125.5, 125.5, 125.4, 124.8, 121.2, 121.13, 121.09, 121.0, 117.4,117.3, 117.0, 116.9, 64.4, 64.3, 64.1, 63.8, 32.5, 32.3 (d, J = 10.0 Hz),11.2 (d, J = 3.6 Hz), 10.5; 31 P NMR (162 MHz, CDCl3) δ 29.59 (s), -6.45 (s);HRMS (EI-TOF) m / z Calcd for C44 H 38 O5P2Si [M] + : 736.2037 found: 736.2034.

[0479] Example 73: I-73

[0480]

[0481] White solid 1 H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H),7.88 (dd, J = 8.0, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.66–7.61 (m, 4H),7.57–7.48 (m, 3H), 7.51–7.43 (m, 4H), 7.32 (dq, J = 7.2, 1.2 Hz, 1H), 7.16(dd, J = 8.0, 7.2 Hz, 1H), 3.00–2.92 (m, 4H), 2.49 (p, J = 7.6 Hz, 2H), 1.86–1.75 (m, 4H), 1.65–1.55 (m, 4H), 1.57–1.51 (m, 1H), 1.54–1.48 (m, 2H), 1.51–1.44 (m, 4H), 1.45 (d, J = 2.0 Hz, 1H), 1.43–1.29 (m, 5H); 13 C NMR (100 MHz,CDCl3) δ 155.4, 154.4, 153.9, 142.1, 140.7, 138.0, 133.3, 132.3, 131.9,128.9, 128.3, 128.0, 126.7, 125.9, 125.4, 122.0, 34.2, 31.6, 31.3, 31.1,27.0, 26.5, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.65 (s), -6.99 (s); HRMS (EI-TOF) m / z Calcd for C 40 H 46 OP2Si [M] + : 632.2793 found: 632.2790.

[0482] Example 74: I-74

[0483]

[0484] White solid 1 H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.88 (dd, J = 8.0, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.66–7.61 (m, 4H), 7.57–7.48 (m, 3H), 7.51–7.43 (m, 4H), 7.32 (dq, J = 7.2, 1.2 Hz, 1H), 7.16 (dd, J = 8.0, 7.2 Hz, 1H), 3.00–2.92 (m, 4H), 2.49 (p, J = 7.6 Hz, 2H), 1.86–1.75 (m, 4H), 1.65–1.55 (m, 4H), 1.57–1.51 (m, 1H), 1.54–1.48 (m, 2H), 1.51–1.44 (m, 4H), 1.45 (d, J = 2.0 Hz, 1H), 1.43–1.29 (m, 5H); 13 C NMR (100 MHz, CDCl3) δ 155.4, 154.4, 153.9, 142.1, 140.7, 138.0, 133.3, 132.3, 131.9,128.9, 128.3, 128.0, 126.7, 125.9, 125.4, 122.0, 34.2, 31.6, 31.3, 31.1,27.0, 26.5, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.65 (s), -6.99 (s); HRMS (EI-TOF) m / z Calcd for C 40 H 46 OP2Si [M] + : 632.2793 found: 632.2795.

[0485] Example 75: I-75

[0486]

[0487] White solid 11H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.66–7.60 (m, 4H), 7.57–7.49 (m, 4H), 7.49–7.43 (m, 4H), 7.34–7.30 (m, 1H), 7.26 (dd, J = 7.2, 6.0 Hz, 1H), 3.26–2.77 (m, 4H), 1.66–1.33 (m, 4H), 1.15 (s, 18H); 13 13C NMR (100 MHz, CDCl3) δ 155.0, 153.9, 149.9, 142.1, 138.0, 135.8, 133.3, 132.3, 131.9, 129.4, 128.9, 128.3, 128.0, 125.9, 122.0, 31.6, 31.3, 29.9, 29.4, 14.7; 31 31P NMR (162 MHz, CDCl3) δ 30.69(s), -7.45 (s); HRMS (EI-TOF) m / z Calcd for C 36 19H 42 31OP2Si [M] + : 580.2480 found: 580.2483.

[0488] Example 76: I-76

[0489]

[0490] White solid, 1 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.66–7.60 (m, 4H), 7.57–7.49 (m, 4H), 7.49–7.43 (m, 4H), 7.34–7.30 (m, 1H), 7.26 (dd, J = 7.2, 6.0 Hz, 1H), 3.26–2.77 (m, 4H), 1.66–1.33 (m, 4H), 1.15 (s, 18H); 13C NMR (100 MHz, CDCl3) δ 155.00, 153.93,149.90, 142.14, 137.99, 135.82, 133.25, 132.33, 131.94, 129.41, 128.87,128.31, 128.03, 125.94, 121.98, 31.57, 31.30, 29.90, 29.36, 14.65δ 155.0,153.9, 149.9, 142.1, 138.0, 135.8, 133.3, 132.3, 131.9, 129.4, 128.9, 128.3, 128.0, 125.9, 122.0, 31.6, 31.3, 29.9, 29.4, 14.7; 31 P NMR (162 MHz, CDCl3) δ30.69 (s), -7.45 (s); HRMS (EI-TOF) m / z Calcd for C 36 H 42 OP2Si [M] + : 580.2480found: 580.2481.

[0491] Example 77: I-77

[0492]

[0493] White solid 1 H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.83 (dd, J = 8.2, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.66–7.61 (m, 4H),7.57–7.49 (m, 3H), 7.49–7.43 (m, 4H), 7.32 (dq, J = 7.2, 1.2 Hz, 1H), 7.16(dd, J = 8.4, 7.2 Hz, 1H), 3.00–2.92 (m, 4H), 2.15–2.04 (m, 2H), 1.50–1.43 (m, 4H), 1.02 (d, J = 7.6 Hz, 12H); 1313C NMR (100 MHz, CDCl3) δ 154.4, 153.9, 150.5, 142.1, 138.4, 138.0, 133.3, 132.3, 131.9, 130.8, 128.9, 128.3, 128.0, 126.7, 125.9, 122.0, 31.6, 31.6, 31.3, 20.2, 14.7; 31 31P NMR (162 MHz, CDCl3) δ 30.72 (s), -7.33 (s); HRMS (EI-TOF) m / z Calcd for C 34 H 38 OP2Si [M] + : 552.2167 found: 552.2160.

[0494] Example 78: I-78

[0495]

[0496] White solid, 1 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.83 (dd, J = 8.2, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.66–7.61 (m, 4H), 7.57–7.49 (m, 3H), 7.49–7.43 (m, 4H), 7.32 (dq, J = 7.2, 1.2 Hz, 1H), 7.16 (dd, J = 8.4, 7.2 Hz, 1H), 3.00–2.92 (m, 4H), 2.15–2.04 (m, 2H), 1.50–1.43 (m, 4H), 1.02 (d, J = 7.6 Hz, 12H); 13 13C NMR (100 MHz, CDCl3) δ 154.4, 153.9, 150.5, 142.1, 138.4, 138.0, 133.3, 132.3, 131.9, 130.8, 128.9, 128.3, 128.0, 126.7, 125.9, 122.0, 31.6, 31.6, 31.3, 20.2, 14.7; 31P NMR (162 MHz, CDCl3) δ 30.72 (s), -7.33 (s); HRMS (EI-TOF) m / z Calcd for C 34 H 38 OP2Si [M] + : 552.2167 found: 552.2166.

[0497] Example 79: I-79

[0498]

[0499] White solid, 1 H NMR (400 MHz, CDCl3) δ 8.05–7.99 (m, 2H), 7.73 (t, J = 1.6 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.64 (dq, J = 5.2, 1.6 Hz, 5H), 7.57–7.49 (m, 4H), 7.49–7.43 (m, 4H), 7.32 (dq, J = 7.2, 1.2 Hz, 1H), 7.23–7.17 (m, 1H), 6.80 (dd, J = 4.8, 1.6 Hz, 1H), 6.70 (dd, J = 2.8, 1.6 Hz, 1H), 6.60 (d, J = 4.8 Hz, 1H), 3.00–2.92 (m, 4H), 1.49–1.43 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 154.0, 153.9, 150.1, 148.6, 148.3, 146.8, 145.3, 142.1, 141.9, 137.9, 133.3, 132.3, 131.9, 129.7, 128.9, 128.3, 128.1, 128.0, 125.9, 125.6, 122.0, 121.4, 117.0, 110.9, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.75 (s), -7.98 (s); HRMS (EI-TOF) m / z Calcd for C 36 H 30 O3P2Si [M] + : 600.1439 found: 600.1440.

[0500] Example 80: I-80

[0501]

[0502] White solid 1 H NMR (400 MHz, CDCl3) δ 8.05–7.99 (m, 2H), 7.73 (t, J = 1.6Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.64 (dq, J = 5.2, 1.6 Hz, 5H), 7.57–7.49(m, 4H), 7.49–7.43 (m, 4H), 7.32 (dq, J = 7.2, 1.2 Hz, 1H), 7.23–7.17 (m,1H), 6.80 (dd, J = 4.8, 1.6 Hz, 1H), 6.70 (dd, J = 2.8, 1.6 Hz, 1H), 6.60 (d,J = 4.8 Hz, 1H), 3.00–2.92 (m, 4H), 1.49–1.43 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 154.0, 153.9, 150.1, 148.6, 148.3, 146.8, 145.3, 142.1, 141.9,137.9, 133.3, 132.3, 131.9, 129.7, 128.9, 128.3, 128.1, 128.0, 125.9, 125.6,122.0, 121.4, 117.0, 110.9, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.75(s), -7.98 (s); HRMS (EI-TOF) m / z Calcd for C 36 H 30 O3P2Si [M] + 600.1439 found: 600.1444.

[0503] Example 81: I-81

[0504]

[0505] White solid 1H NMR (400 MHz, CDCl3) δ 7.62–7.34 (m, 6H), 7.34–7.13 (m,4H), 7.08 (dd, J = 12.0, 4.4 Hz, 5H), 7.03–6.79 (m, 6H), 6.70 (t, J = 7.6 Hz,2H), 3.69–3.50 (m, 2H), 3.28–3.03 (m, 2H), 2.31 (s, 3H), 2.25 (s, 3H), 1.52–1.33 (m, 1H), 1.20–1.09 (m, 1H), 1.07–0.76 (m, 2H); 13 C NMR (100 MHz, CDCl3) δ157.8, 157.7, 155.2, 155.0, 147.6, 147.0, 142.20, 142.17, 142.1, 142.0,141.7, 141.6, 137.6, 137.5, 136.4, 135.9, 135.8, 134.7, 134.4, 134.3, 133.8,133.7, 133.6, 133.4, 132.9, 132.8, 132.4, 132.01, 131.95, 131.91, 131.85,131.34, 131.31, 131.1, 131.0, 130.29, 130.27, 130.2, 130.1, 129.4, 129.0, 128.9, 128.7, 128.64, 128.61, 128.5, 128.3, 128.2, 127.8, 127.7, 126.5, 32.54, 32.45, 32.3, 29.7, 21.3, 21.2, 11.32, 11.28, 10.4; 31 P NMR (162 MHz, CDCl3) δ 30.26 (s), -7.96 (s); HRMS (EI-TOF) m / z Calcd for C 42 H 38 OP2Si [M] + :648.2240 found: 648.2243.

[0506] Example 82: I-82

[0507]

[0508] White solid 1H NMR (400 MHz, CDCl3) δ 7.62–7.34 (m, 6H), 7.34–7.13 (m,4H), 7.08 (dd, J = 12.0, 4.4 Hz, 5H), 7.03–6.79 (m, 6H), 6.70 (t, J = 7.6 Hz,2H), 3.69–3.50 (m, 2H), 3.28–3.03 (m, 2H), 2.31 (s, 3H), 2.25 (s, 3H), 1.52–1.33 (m, 1H), 1.20–1.09 (m, 1H), 1.07–0.76 (m, 2H); 13 C NMR (100 MHz, CDCl3) δ157.8, 157.7, 155.2, 155.0, 147.6, 147.0, 142.20, 142.17, 142.1, 142.0,141.7, 141.6, 137.6, 137.5, 136.4, 135.9, 135.8, 134.7, 134.4, 134.3, 133.8,133.7, 133.6, 133.4, 132.9, 132.8, 132.4, 132.01, 131.95, 131.91, 131.85,131.34, 131.31, 131.1, 131.0, 130.29, 130.27, 130.2, 130.1, 129.4, 129.0, 128.9, 128.7, 128.64, 128.61, 128.5, 128.3, 128.2, 127.8, 127.7, 126.5, 32.54, 32.45, 32.3, 29.7, 21.3, 21.2, 11.32, 11.28, 10.4; 31 P NMR (162 MHz, CDCl3) δ 30.26 (s), -7.96 (s); HRMS (EI-TOF) m / z Calcd for C 42 H 38 OP2Si [M] + 648.2240 found: 648.2247.

[0509] Example 83: I-83

[0510]

[0511] White solid 1H NMR (400 MHz, CDCl3) δ 7.57–7.43 (m, 4H), 7.38 (d, J = 5.2Hz, 2H), 7.32–7.16 (m, 4H), 7.11 (t, J = 4.8 Hz, 2H), 7.03 (d, J = 8.0 Hz,4H), 6.94 (dd, J = 12.8, 7.6 Hz, 1H), 6.80 (t, J = 12.0 Hz, 2H), 6.72 (t, J =7.6 Hz, 2H), 6.61 (d, J = 8.2 Hz, 1H), 3.76 (s, 3H), 3.72–3.49 (m, 5H), 3.28–3.16 (m, 1H), 3.16–3.01 (m, 1H), 1.44–1.31 (m, 1H), 1.21–1.10 (m, 1H), 1.06 –0.79 (m, 3H); 13 C NMR (100 MHz, CDCl3) δ 159.5, 159.4, 157.7, 157.6, 155.2,155.0, 147.2, 146.7, 142.23, 142.20, 142.16, 142.09, 142.05, 137.5, 136.4,135.2, 135.0, 134.5, 134.3, 134.4, 133.54, 133.46, 132.5, 132.0, 131.91,131.89, 131.8, 131.32, 131.30, 131.08, 131.05, 130.4, 130.3, 130.2, 130.0,129.9, 129.41, 129.36, 128.8, 128.7, 128.6, 128.5, 128.3, 128.2, 127.8,127.7, 126.4, 113.8, 113.7, 113.5, 113.4, 55.1, 54.9, 32.5, 32.4, 11.4 (d, J= 3.6 Hz), 10.4; 31 P NMR (162 MHz, CDCl3) δ 30.24 (s), -9.80 (s); HRMS (EI-TOF) m / z Calcd for C 42 H 38 O3P2Si [M] + : 680.2138 found: 680.2128.

[0512] Example 84: I-84

[0513]

[0514] White solid 1 H NMR (400 MHz, CDCl3) δ 7.57–7.43 (m, 4H), 7.38 (d, J = 5.2Hz, 2H), 7.32–7.16 (m, 4H), 7.11 (t, J = 4.8 Hz, 2H), 7.03 (d, J = 8.0 Hz, 4H), 6.94 (dd, J = 12.8, 7.6 Hz, 1H), 6.80 (t, J = 12.0 Hz, 2H), 6.72 (t, J =7.6 Hz, 2H), 6.61 (d, J = 8.2 Hz, 1H), 3.76 (s, 3H), 3.72–3.49 (m, 5H), 3.28–3.16 (m, 1H), 3.16–3.01 (m, 1H), 1.44–1.31 (m, 1H), 1.21–1.10 (m, 1H), 1.06 –0.79 (m, 3H); 13 C NMR (100 MHz, CDCl3) δ 159.5, 159.4, 157.7, 157.6, 155.2,155.0, 147.2, 146.7, 142.23, 142.20, 142.16, 142.09, 142.05, 137.5, 136.4,135.2, 135.0, 134.5, 134.3, 134.4, 133.54, 133.46, 132.5, 132.0, 131.91,131.89, 131.8, 131.32, 131.30, 131.08, 131.05, 130.4, 130.3, 130.2, 130.0,129.9, 129.41, 129.36, 128.8, 128.7, 128.6, 128.5, 128.3, 128.2, 127.8,127.7, 126.4, 113.8, 113.7, 113.5, 113.4, 55.1, 54.9, 32.5, 32.4, 11.4 (d, J= 3.6 Hz), 10.4; 31P NMR (162 MHz, CDCl3) δ 30.24 (s), -9.80 (s); HRMS (EI-TOF) m / z Calcd for C 42 H 38 O3P2Si [M] + 680.2138 found: 680.2136.

[0515] Example 85: I-85

[0516]

[0517] White solid 1 H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.71–7.66 (m, 5H), 7.66–7.62 (m, 4H), 7.62–7.57 (m, 4H), 7.56–7.49 (m, 3H), 7.49–7.42 (m, 8H), 7.42–7.37 (m, 6H), 7.34–7.29 (m, 1H), 7.22–7.16 (m, 1H), 3.29–2.58 (m, 4H), 1.75–1.17 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 153.9, 153.7, 151.6, 143.6, 142.1, 141.00, 140.97, 138.0,137.7, 135.3, 133.3, 132.3, 131.9, 130.0, 129.3, 128.9, 128.33, 128.31,128.1, 128.03, 128.00, 127.5, 125.9, 122.0, 31.6, 31.3, 14.7; 31 P NMR (162MHz, CDCl3) δ 30.70 (s), -7.45 (s); HRMS (EI-TOF) m / z Calcd for C 52 H 42 OP2Si [M] + 772.2480 found: 772.2485.

[0518] Example 86: I-86

[0519]

[0520] White solid 1 H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.71–7.66 (m, 5H), 7.66–7.62 (m, 4H), 7.62–7.57 (m, 4H), 7.56–7.49 (m, 3H), 7.49–7.42 (m, 8H), 7.42–7.37 (m, 6H), 7.34–7.29 (m, 1H), 7.22–7.16 (m, 1H), 3.29–2.58 (m, 4H), 1.75–1.17 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 153.9, 153.7, 151.6, 143.6, 142.1, 141.00, 140.97, 138.0,137.7, 135.3, 133.3, 132.3, 131.9, 130.0, 129.3, 128.9, 128.33, 128.31,128.1, 128.03, 128.00, 127.5, 125.9, 122.0, 31.6, 31.3, 14.7; 31 P NMR (162MHz, CDCl3) δ 30.70 (s), -7.45 (s); HRMS (EI-TOF) m / z Calcd for C 52 H 42 OP2Si [M] + 772.2480 found: 772.2487.

[0521] Example 87: I-87

[0522]

[0523] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.67–7.61 (m, 3.00 (s, 12H), 2.98–2.92 (m, 4H), 1.52–1.39 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 153.9, 153.7, 151.5, 151.4, 143.6,142.1, 138.0, 135.9, 133.3, 132.3, 131.9, 130.00, 129.96, 128.9, 128.3,128.1, 128.0, 125.9, 122.0, 114.0, 40.3, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.74 (s), -8.96 (s); HRMS (EI-TOF) m / z Calcd for C 44 H 44 N2OP2Si [M] + 706.2698 found: 706.2690.

[0524] Example 88: I-88

[0525]

[0526] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.67–7.61 (m, 3.00 (s, 12H), 2.98–2.92 (m, 4H), 1.52–1.39 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 153.9, 153.7, 151.5, 151.4, 143.6,142.1, 138.0, 135.9, 133.3, 132.3, 131.9, 130.00, 129.96, 128.9, 128.3,128.1, 128.0, 125.9, 122.0, 114.0, 40.3, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.74 (s), -8.96 (s); HRMS (EI-TOF) m / z Calcd for C 44 H 44 N2OP2Si [M] + 706.2698 found: 706.2694.

[0527] Example 89: I-89

[0528]

[0529] White solid 11H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.67–7.60 (m, 4H), 7.56–7.41 (m, 11H), 7.34–7.29 (m, 1H), 7.18–7.13 (m, 4H), 3.18–2.68 (m, 4H), 1.78–1.14 (m, 4H); 13 13C NMR (100 MHz, CDCl3) δ 163.4, 153.9, 153.7, 151.4, 143.7, 142.1, 138.0, 136.9, 134.2, 133.3, 132.3, 131.9, 130.0, 128.9, 128.3, 128.1, 128.0, 125.9, 122.0, 116.3, 31.6, 31.3, 14.7; 31 31P NMR (162 MHz, CDCl3) δ 30.70 (s), -6.33 (s); 19 19F NMR (375 MHz, CDCl3) δ -107.80, -108.12; HRMS (EI-TOF) m / z Calcd for C 40 H 32 F2OP2Si [M] + : 656.1666 found: 656.1670.

[0530] Example 90: I-90

[0531]

[0532] White solid, 1 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.67–7.60 (m, 4H), 7.56–7.4 (m, 11H), 7.34–7.29 (m, 1H), 7.18–7.13 (m, 4H), 3.18–2.68 (m, 4H), 1.78–1.14 (m, 4H); 1313C NMR (100 MHz, CDCl3) δ 163.4, 153.9, 153.7, 151.4, 143.7, 142.1, 138.0, 136.9, 134.2, 133.3, 132.3, 131.9, 130.0, 128.9, 128.3, 128.1, 128.0, 125.9, 122.0, 116.3, 31.6, 31.3, 14.7; 31 31P NMR (162 MHz, CDCl3) δ 30.70 (s), -6.33 (s); 19 19F NMR (375 MHz, CDCl3) δ -107.80, -108.12; HRMS (EI-TOF) m / z Calcd for C 40 H 32 F2OP2Si [M] + : 656.1666 found: 656.1669.

[0533] Example 91: I-91

[0534]

[0535] White solid, 1 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.66–7.61 (m, 4H), 7.57–7.49 (m, 3H), 7.49–7.37 (m, 12H), 7.34–7.27 (m, 1H), 7.23–7.17 (m, 1H), 3.21–2.72 (m, 4H), 1.61–0.99 (m, 4H); 13 13C NMR (100 MHz, CDCl3) δ 153.9, 153.7, 151.5, 143.6, 142.1, 138.0, 136.6, 136.3, 135.2, 133.3, 132.3, 131.9, 130.0, 129.5, 128.9, 128.3, 128.1, 128.0, 125.9, 122.0, 31.6, 31.3, 14.7; 31P NMR(162 MHz, CDCl3) δ 30.69 (s), -6.35 (s); HRMS (EI-TOF) m / z Calcd forC 40 H 32 Cl2OP2Si [M] + 688.1075 found: 688.1080.

[0536] Example 92: I-92

[0537]

[0538] White solid 1 H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.66–7.61 (m, 4H),7.57–7.49 (m, 3H), 7.49–7.37 (m, 12H), 7.34–7.27 (m, 1H), 7.23–7.17 (m, 1H),3.21–2.72 (m, 4H), 1.61–0.99 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 153.9, 153.7,151.5, 143.6, 142.1, 138.0, 136.6, 136.3, 135.2, 133.3, 132.3, 131.9, 130.0,129.5, 128.9, 128.3, 128.1, 128.0, 125.9, 122.0, 31.6, 31.3, 14.7; 31 P NMR(162 MHz, CDCl3) δ 30.69 (s), -6.35 (s); HRMS (EI-TOF) m / z Calcd forC 40 H 32 Cl2OP2Si [M] + 688.1075 found: 688.1077.

[0539] Example 93: I-93

[0540]

[0541] White solid 11H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.67–7.59 (m, 8H), 7.56–7.49 (m, 7H), 7.49–7.42 (m, 4H), 7.34–7.28 (m, 1H), 7.22–7.17 (m, 1H), 3.20–2.72 (m, 4H), 1.71–1.23 (m, 4H); 13 13C NMR (100 MHz, CDCl3) 13 13C NMR (125MHz, Common NMR Solvents) δ 153.9, 153.7, 151.6, 143.6, 142.1, 138.0, 137.0, 135.5, 133.3, 132.3, 131.9, 131.5, 130.0, 128.9, 128.3, 128.1, 128.0, 127.1, 125.9, 124.0, 122.0, 31.6, 31.3, 14.7; 31 31P NMR (162 MHz, CDCl3) δ 30.72 (s), -7.45 (s); 19 19F NMR (375 MHz, CDCl3) δ -63.37; HRMS (EI-TOF) m / z Calcd for C 42 18 32 6FOP2Si [M] + : 756.1602 found: 756.1600.

[0542] Example 94: I-94

[0543]

[0544] White solid, 11H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.67–7.59 (m, 8H), 7.56–7.49 (m, 7H), 7.49–7.42 (m, 4H), 7.34–7.28 (m, 1H), 7.22–7.17 (m, 1H), 3.20–2.72 (m, 4H), 1.71–1.23 (m, 4H); 13 13C NMR (100 MHz, CDCl3) 13 13C NMR (125MHz, Common NMR Solvents) δ 153.9, 153.7, 151.6, 143.6, 142.1, 138.0, 137.0, 135.5, 133.3, 132.3, 131.9, 131.5, 130.0, 128.9, 128.3, 128.1, 128.0, 127.1, 125.9, 124.0, 122.0, 31.6, 31.3, 14.7; 31 31P NMR (162 MHz, CDCl3) δ 30.72 (s), -7.45 (s); 19 19F NMR (375 MHz, CDCl3) δ -63.37; HRMS (EI-TOF) m / z Calcd for C 42 H 32 F6OP2Si [M] + : 756.1602 found: 756.1605.

[0545] Example 95: I-95

[0546]

[0547] White solid 1H NMR (400 MHz, CDCl3) δ 7.56–7.36 (m, 6H), 7.25 (d, J = 7.6Hz, 4H), 7.21–7.14 (m, 4H), 7.11–7.03 (m, 5H), 6.97 (dd, J = 12.8, 7.2 Hz,1H), 6.90 (q, J = 4.0 Hz, 1H), 6.75 (d, J = 7.6 Hz, 2H), 3.67–3.48 (m, 2H),3.25–3.14 (m, 1H), 3.13–3.00 (m, 1H), 1.58–1.48 (m, 1H), 1.29 (s, 9H), 1.22(s, 9H), 1.16–1.07 (m, 1H), 1.05–0.87 (m, 2H); 13 C NMR (100 MHz, CDCl3) δ157.8, 157.7, 155.1, 155.0, 150.8, 150.5, 147.5, 147.0, 141.8 (d, J = 7.5Hz), 137.5, 136.5, 135.6, 135.5, 134.8, 134.7, 133.8, 133.3, 133.1, 132.9,132.7, 132.2, 132.0 (d, J = 1.9 Hz), 131.90, 131.88, 131.3 (d, J = 2.7 Hz),131.1 (d, J = 2.8 Hz), 130.6 (d, J = 1.0 Hz), 130.5, 130.3, 129.5, 128.7,128.6, 128.3, 128.2, 127.9, 127.8, 126.5, 125.1 (d, J = 6.3 Hz), 124.7 (d, J= 6.7 Hz), 34.5, 34.4, 32.5, 32.4, 32.3, 31.2 (d, J = 4.0 Hz), 11.0 (d, J =3.7 Hz), 10.5; 31 P NMR (162 MHz, CDCl3) δ 30.51 (s), -7.90 (s); HRMS (ESI-TOF)m / z Calcd for C 48 H 51 OP2Si [M+H] + : 733.3179 found: 733.3180.

[0548] Example 96: I-96

[0549]

[0550] White solid 1 H NMR (400 MHz, CDCl3) δ 7.56–7.36 (m, 6H), 7.25 (d, J = 7.6Hz, 4H), 7.21–7.14 (m, 4H), 7.11–7.03 (m, 5H), 6.97 (dd, J = 12.8, 7.2 Hz,1H), 6.90 (q, J = 4.0 Hz, 1H), 6.75 (d, J = 7.6 Hz, 2H), 3.67–3.48 (m, 2H), 3.25–3.14 (m, 1H), 3.13–3.00 (m, 1H), 1.58–1.48 (m, 1H), 1.29 (s, 9H), 1.22(s, 9H), 1.16–1.07 (m, 1H), 1.05–0.87 (m, 2H); 13 C NMR (100 MHz, CDCl3) δ157.8, 157.7, 155.1, 155.0, 150.8, 150.5, 147.5, 147.0, 141.8 (d, J = 7.5Hz), 137.5, 136.5, 135.6, 135.5, 134.8, 134.7, 133.8, 133.3, 133.1, 132.9,132.7, 132.2, 132.0 (d, J = 1.9 Hz), 131.90, 131.88, 131.3 (d, J = 2.7 Hz),131.1 (d, J = 2.8 Hz), 130.6 (d, J = 1.0 Hz), 130.5, 130.3, 129.5, 128.7,128.6, 128.3, 128.2, 127.9, 127.8, 126.5, 125.1 (d, J = 6.3 Hz), 124.7 (d, J= 6.7 Hz), 34.5, 34.4, 32.5, 32.4, 32.3, 31.2 (d, J = 4.0 Hz), 11.0 (d, J =3.7 Hz), 10.5; 31P NMR (162 MHz, CDCl3) δ 30.51 (s), -7.90 (s); HRMS (ESI-TOF)m / z Calcd for C 48 H 51 OP2Si [M+H] + 733.3179 found: 733.3184.

[0551] Example 97: I-97

[0552]

[0553] White solid 1 H NMR (400 MHz, CDCl3) δ 7.59–7.43 (m, 4H), 7.44–7.35 (m,2H), 7.34–7.16 (m, 4H), 7.16–6.87 (m, 11H), 6.84 (d, J = 6.8 Hz, 1H), 6.71(t, J = 5.2 Hz, 1H), 6.63 (d, J = 8.8 Hz, 1H), 3.80–3.43 (m, 2H), 3.29–2.99(m, 2H), 2.24 (s, 3H), 2.10 (s, 3H), 1.45–1.33 (m, 2H), 1.24–1.12 (m, 1H), 1.08–0.81 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 157.8, 157.7, 154.9, 154.8,148.1, 147.6, 142.31, 142.28, 142.2, 142.1, 141.4, 141.3, 139.4, 139.3,137.6, 137.5, 137.4, 137.3, 137.2, 137.1, 137.0, 136.5, 134.8, 134.5, 134.4,133.6, 133.41, 133.35, 133.2, 132.6, 132.0, 131.91, 131.89, 131.8, 131.33,131.30, 131.12, 131.09, 130.9, 130.41, 130.39, 130.2, 130.0, 129.8, 129.7,129.5, 129.4, 129.0, 128.6, 128.49, 128.46, 128.3, 128.2, 127.94, 127.88,127.81, 127.76, 127.7, 127.6, 126.6, 32.51, 32.50 (d, J = 11.0 Hz), 21.42,21.35, 11.5 (d, J = 3.7 Hz), 10.3; 31 P NMR (162 MHz, CDCl3) δ 30.45 (s), -6.12(s); HRMS (EI-TOF) m / z Calcd for C 42 H 38 OP2Si [M] + Found: 648.2240.

[0554] Example 98: I-98

[0555]

[0556] White solid 1H NMR (400 MHz, CDCl3) δ 7.59–7.43 (m, 4H), 7.44–7.35 (m,2H), 7.34–7.16 (m, 4H), 7.16–6.87 (m, 11H), 6.84 (d, J = 6.8 Hz, 1H), 6.71(t, J = 5.2 Hz, 1H), 6.63 (d, J = 8.8 Hz, 1H), 3.80–3.43 (m, 2H), 3.29–2.99(m, 2H), 2.24 (s, 3H), 2.10 (s, 3H), 1.45–1.33 (m, 2H), 1.24–1.12 (m, 1H),1.08–0.81 (m, 2H); 13 C NMR (100 MHz, CDCl3) δ 157.8, 157.7, 154.9, 154.8,148.1, 147.6, 142.31, 142.28, 142.2, 142.1, 141.4, 141.3, 139.4, 139.3,137.6, 137.5, 137.4, 137.3, 137.2, 137.1, 137.0, 136.5, 134.8, 134.5, 134.4,133.6, 133.41, 133.35, 133.2, 132.6, 132.0, 131.91, 131.89, 131.8, 131.33,131.30, 131.12, 131.09, 130.9, 130.41, 130.39, 130.2, 130.0, 129.8, 129.7,129.5, 129.4, 129.0, 128.6, 128.49, 128.46, 128.3, 128.2, 127.94, 127.88,127.81, 127.76, 127.7, 127.6, 126.6, 32.51, 32.50 (d, J = 11.0 Hz), 21.42,21.35, 11.5 (d, J = 3.7 Hz), 10.3; 31 P NMR (162 MHz, CDCl3) δ 30.45 (s), -6.12(s); HRMS (EI-TOF) m / z Calcd for C 42 H 38 OP2Si [M] +648.2240 found: 648.2241.

[0557] Example 99: I-99

[0558]

[0559] White solid 1 H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.66–7.59 (m, 4H),7.57–7.49 (m, 3H), 7.49–7.42 (m, 4H), 7.34–7.30 (m, 1H), 7.28 (d, J = 7.6 Hz,2H), 7.23–7.18 (m, 3H), 7.18–7.13 (m, 2H), 6.99 (td, J = 2.4, 0.8 Hz, 2H),3.05–2.80 (m, 6H), 1.61–1.38 (m, 4H), 1.27 (d, J = 6.8 Hz, 12H); 13 C NMR (100MHz, CDCl3) δ 153.9, 153.7, 150.7, 150.6, 143.6, 142.1, 138.0, 137.7, 133.3,133.2, 132.3, 131.9, 130.2, 130.0, 128.9, 128.8, 128.3, 128.1, 128.0, 126.5,125.9, 122.0, 32.8, 31.6, 31.3, 23.9, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.55(s), -6.24 (s); HRMS (EI-TOF) m / z Calcd for C 46 H 46 OP2Si [M] + 704.2793 found:704.2800.

[0560] Example 100: I-100

[0561]

[0562] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.66–7.59 (m, 4H),7.57–7.49 (m, 3H), 7.49–7.42 (m, 4H), 7.34–7.30 (m, 1H), 7.28 (d, J = 7.6 Hz,2H), 7.23–7.18 (m, 3H), 7.18–7.13 (m, 2H), 6.99 (td, J = 2.4, 0.8 Hz, 2H),3.05–2.80 (m, 6H), 1.61–1.38 (m, 4H), 1.27 (d, J = 6.8 Hz, 12H); 13 C NMR (100MHz, CDCl3) δ 153.9, 153.7, 150.7, 150.6, 143.6, 142.1, 138.0, 137.7, 133.3,133.2, 132.3, 131.9, 130.2, 130.0, 128.9, 128.8, 128.3, 128.1, 128.0, 126.5,125.9, 122.0, 32.8, 31.6, 31.3, 23.9, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.55(s), -6.24 (s); HRMS (EI-TOF) m / z Calcd for C 46 H 46 OP2Si [M] + 704.2793 found: 704.2795.

[0563] Example 101: I-101

[0564]

[0565] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.66–7.60 (m, 4H),7.57–7.49 (m, 3H), 7.49–7.42 (m, 4H), 7.34–7.30 (m, 1H), 7.29–7.15 (m, 9H),3.08–2.82 (m, 4H), 1.54–1.40 (m, 4H), 1.34 (s, 18H); 13 C NMR (100 MHz, CDCl3)δ 153.9, 153.7, 150.6, 143.6, 142.1, 138.0, 137.2, 133.7, 133.3, 132.3,131.9, 130.4, 130.0, 128.9, 128.8, 128.3, 128.1, 128.0, 126.3, 125.9, 122.0,34.6, 31.6, 31.30, 31.25, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.57 (s), -6.22(s); HRMS (EI-TOF) m / z Calcd for C 48 H 50 OP2Si [M] + 732.3106 found: 732.3107.

[0566] Example 102: I-102

[0567]

[0568] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.66–7.60 (m, 4H),7.57–7.49 (m, 3H), 7.49–7.42 (m, 4H), 7.34–7.30 (m, 1H), 7.29–7.15 (m, 9H),3.08–2.82 (m, 4H), 1.54–1.40 (m, 4H), 1.34 (s, 18H); 13 C NMR (100 MHz, CDCl3)δ 153.9, 153.7, 150.6, 143.6, 142.1, 138.0, 137.2, 133.7, 133.3, 132.3,131.9, 130.4, 130.0, 128.9, 128.8, 128.3, 128.1, 128.0, 126.3, 125.9, 122.0,34.6, 31.6, 31.30, 31.25, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.57 (s), -6.22(s); HRMS (EI-TOF) m / z Calcd for C 48 H 50 OP2Si [M] + 732.3106 found: 732.3103.

[0569] Example 103: I-103

[0570]

[0571] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.82 (d, J = 2.0 Hz, 2H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2Hz, 1H), 7.66–7.62 (m, 4H), 7.62–7.57 (m, 4H), 7.57–7.49 (m, 3H), 7.49–7.42(m, 4H), 7.35–7.29 (m, 1H), 7.26–7.21 (m, 2H), 7.21–7.16 (m, 1H), 3.08–2.74(m, 4H), 1.49–1.43 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 153.9, 153.7, 150.5,143.7, 142.1, 138.0, 137.9, 133.7, 133.4, 133.3, 132.3, 131.9, 130.0, 129.6,129.0, 128.9, 128.3, 128.1, 128.0, 126.5, 125.9, 123.9, 122.0, 31.6, 31.3,14.7; 31 P NMR (162 MHz, CDCl3) δ 30.45 (s), -6.13 (s); 19 F NMR (375 MHz, CDCl3)δ -63.18; HRMS (EI-TOF) m / z Calcd for C 42 H 32 F6OP2Si [M] + 756.1602 found:756.1605.

[0572] Example 104: I-104

[0573]

[0574] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.82 (d, J = 2.0 Hz, 2H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2Hz, 1H), 7.66–7.62 (m, 4H), 7.62–7.57 (m, 4H), 7.57–7.49 (m, 3H), 7.49–7.42(m, 4H), 7.35–7.29 (m, 1H), 7.26–7.21 (m, 2H), 7.21–7.16 (m, 1H), 3.08–2.74(m, 4H), 1.49–1.43 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 153.9, 153.7, 150.5,143.7, 142.1, 138.0, 137.9, 133.7, 133.4, 133.3, 132.3, 131.9, 130.0, 129.6,129.0, 128.9, 128.3, 128.1, 128.0, 126.5, 125.9, 123.9, 122.0, 31.6, 31.3,14.7; 31 P NMR (162 MHz, CDCl3) δ 30.45 (s), -6.13 (s); 19 F NMR (375 MHz, CDCl3)δ -63.37; HRMS (EI-TOF) m / z Calcd for C 42 H 32 F6OP2Si [M] + 756.1602 found:756.1603.

[0575] Example 105: I-105

[0576]

[0577] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.66–7.60 (m, 4H),7.56–7.49 (m, 3H), 7.49–7.42 (m, 4H), 7.31 (t, J = 7.6 Hz, 3H), 7.22–7.17 (m,1H), 7.13–7.08 (m, 2H), 6.96 (t, J = 2.4 Hz, 2H), 6.88–6.82 (m, 2H), 3.82 (s,6H), 3.00–2.92 (m, 4H), 1.49–1.43 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 161.7,153.9, 153.8, 150.2, 143.6, 142.1, 138.2, 138.0, 133.3, 132.3, 131.9, 130.0,129.1, 128.9, 128.3, 128.1, 128.0, 127.6, 125.9, 122.0, 117.5, 115.5, 55.5,31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.34 (s), -6.32 (s); HRMS (EI-TOF) m / z Calcd for C 42 H 38 O3P2Si [M] + 680.2065 found: 680.2072.

[0578] Example 106: I-106

[0579]

[0580] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.66–7.60 (m, 4H),7.56–7.49 (m, 3H), 7.49–7.42 (m, 4H), 7.31 (t, J = 7.6 Hz, 3H), 7.22–7.17 (m,1H), 7.13–7.08 (m, 2H), 6.96 (t, J = 2.4 Hz, 2H), 6.88–6.82 (m, 2H), 3.82 (s,6H), 3.00–2.92 (m, 4H), 1.49–1.43 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 161.7,153.9, 153.8, 150.2, 143.6, 142.1, 138.2, 138.0, 133.3, 132.3, 131.9, 130.0,129.1, 128.9, 128.3, 128.1, 128.0, 127.6, 125.9, 122.0, 117.5, 115.5, 55.5,31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.34 (s), -6.32 (s); HRMS (EI-TOF) m / z Calcd for C 42 H 38 O3P2Si [M] + 680.2065 found: 680.2070.

[0581] Example 107: I-107

[0582]

[0583] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.67–7.60 (m, 4H),7.57–7.49 (m, 3H), 7.49–7.43 (m, 4H), 7.38–7.27 (m, 3H), 7.22–7.15 (m, 1H),7.14–7.06 (m, 2H), 6.85 (t, J = 2.4 Hz, 2H), 6.81–6.75 (m, 2H), 4.70–4.60 (m, 2H), 3.00–2.92 (m, 4H), 1.49–1.43 (m, 4H), 1.33 (d, J = 5.6 Hz, 12H); 13 C NMR(100 MHz, CDCl3) δ 159.8, 153.9, 153.8, 150.2, 143.6, 142.1, 138.3, 138.0,133.3, 132.3, 131.9, 130.0, 129.3, 128.9, 128.3, 128.1, 128.0, 127.6, 125.9,122.0, 119.7, 118.4, 70.1, 31.6, 31.3, 21.9, 14.7; 31 P NMR (162 MHz, CDCl3) δ30.35 (s), -6.42 (s); HRMS (EI-TOF) m / z Calcd for C 46 H 46 O3P2Si [M] + 736.2691 found: 736.2690.

[0584] Example 108: I-108

[0585]

[0586] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.67–7.60 (m, 4H),7.57–7.49 (m, 3H), 7.49–7.43 (m, 4H), 7.38–7.27 (m, 3H), 7.22–7.15 (m, 1H),7.14–7.06 (m, 2H), 6.85 (t, J = 2.4 Hz, 2H), 6.81–6.75 (m, 2H), 4.70–4.60 (m, 2H), 3.00–2.92 (m, 4H), 1.49–1.43 (m, 4H), 1.33 (d, J = 5.6 Hz, 12H); 13 C NMR(100 MHz, CDCl3) δ 159.8, 153.9, 153.8, 150.2, 143.6, 142.1, 138.3, 138.0,133.3, 132.3, 131.9, 130.0, 129.3, 128.9, 128.3, 128.1, 128.0, 127.6, 125.9,122.0, 119.7, 118.4, 70.1, 31.6, 31.3, 21.9, 14.7; 31 P NMR (162 MHz, CDCl3) δ30.35 (s), -6.42 (s); HRMS (EI-TOF) m / z Calcd for C 46 H 46 O3P2Si [M] + 736.2691 found: 736.2696.

[0587] Example 109: I-109

[0588]

[0589] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.67–7.60 (m, 4H),7.57–7.49 (m, 3H), 7.49–7.39 (m, 8H), 7.39–7.24 (m, 9H), 7.22–7.16 (m, 1H),7.13–7.08 (m, 2H), 6.99–6.93 (m, 2H), 6.92 (t, J = 2.4 Hz, 2H), 5.07 (d, J =0.8 Hz, 4H), 3.00–2.92 (m, 4H), 1.49–1.43 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ160.6, 153.9, 153.8, 150.2, 143.6, 142.1, 138.1, 138.0, 136.9, 133.3, 132.3,131.9, 130.9, 130.0, 129.2, 128.9, 128.6, 128.4, 128.3, 128.1, 128.0, 127.6,125.9, 122.0, 118.9, 117.1, 70.0, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ30.49 (s), -6.47 (s); HRMS (EI-TOF) m / z Calcd for C 54 H 46 O3P2Si [M] + 832.2691 found: 832.2694.

[0590] Example 110: I-110

[0591]

[0592] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.67–7.60 (m, 4H),7.57–7.49 (m, 3H), 7.49–7.39 (m, 8H), 7.39–7.24 (m, 9H), 7.22–7.16 (m, 1H),7.13–7.08 (m, 2H), 6.99–6.93 (m, 2H), 6.92 (t, J = 2.4 Hz, 2H), 5.07 (d, J =0.8 Hz, 4H), 3.00–2.92 (m, 4H), 1.49–1.43 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ160.6, 153.9, 153.8, 150.2, 143.6, 142.1, 138.1, 138.0, 136.9, 133.3, 132.3,131.9, 130.9, 130.0, 129.2, 128.9, 128.6, 128.4, 128.3, 128.1, 128.0, 127.6,125.9, 122.0, 118.9, 117.1, 70.0, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ30.49 (s), -6.47 (s); HRMS (EI-TOF) m / z Calcd for C 54 H 46 O3P2Si [M] + 832.2691 found: 832.2698.

[0593] Example 111: I-111

[0594]

[0595] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.67–7.60 (m, 4H),7.56–7.49 (m, 3H), 7.49–7.42 (m, 4H), 7.39 (dd, J = 7.6, 6.8 Hz, 2H), 7.34–7.29 (m, 1H), 7.24 (t, J = 2.4 Hz, 2H), 7.21–7.17 (m, 1H), 7.17–7.13 (m, 2H), 7.12–7.07 (m, 2H), 3.00–2.92 (m, 4H), 1.52–1.34 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 153.9, 153.8, 151.7, 150.4, 143.6, 142.1, 138.1, 138.0, 133.3, 132.3, 131.9, 130.0, 129.3, 128.9, 128.3, 128.1, 128.0, 127.6, 125.9, 124.6,122.6, 122.0, 120.4, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.15 (s), -6.16 (s); 19 F NMR (375 MHz, CDCl3) δ -58.42; HRMS (EI-TOF) m / z Calcd forC 42 H 32 F6O3P2Si [M] + 788.1500 found: 788.1499.

[0596] Example 112: I-112

[0597]

[0598] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.67–7.60 (m, 4H),7.56–7.49 (m, 3H), 7.49–7.42 (m, 4H), 7.39 (dd, J = 7.6, 6.8 Hz, 2H), 7.34–7.29 (m, 1H), 7.24 (t, J = 2.4 Hz, 2H), 7.21–7.17 (m, 1H), 7.17–7.13 (m, 2H), 7.12–7.07 (m, 2H), 3.00–2.92 (m, 4H), 1.52–1.34 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 153.9, 153.8, 151.7, 150.4, 143.6, 142.1, 138.1, 138.0, 133.3, 132.3, 131.9, 130.0, 129.3, 128.9, 128.3, 128.1, 128.0, 127.6, 125.9, 124.6,122.6, 122.0, 120.4, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.15 (s), -6.16 (s); 19 F NMR (375 MHz, CDCl3) δ -58.42; HRMS (EI-TOF) m / z Calcd forC 42 H 32 F6O3P2Si [M] + 788.1500 found: 788.1497.

[0599] Example 113: I-113

[0600]

[0601] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.66–7.61 (m, 4H),7.57–7.48 (m, 3H), 7.48–7.43 (m, 4H), 7.34–7.29 (m, 1H), 7.23–7.16 (m, 1H),6.93 (d, J = 2.4 Hz, 4H), 6.90 (t, J = 2.4 Hz, 2H), 3.00–2.92 (m, 4H), 2.19(s, 12H), 1.49–1.43 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 153.9, 153.7, 150.0,143.7, 142.1, 140.4, 138.0, 137.0, 133.3, 132.3, 131.9, 131.0, 130.9, 130.0,128.9, 128.3, 128.1, 128.0, 125.9, 122.0, 31.6, 31.3, 21.1, 14.7; 31 P NMR (162MHz, CDCl3) δ 31.34 (s), -5.49 (s); HRMS (EI-TOF) m / z Calcd for C 44 H 42 OP2Si [M] + Found: 676.2480; Found: 676.2477.

[0602] Example 114: I-114

[0603]

[0604] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.66–7.61 (m, 4H),7.57–7.48 (m, 3H), 7.48–7.43 (m, 4H), 7.34–7.29 (m, 1H), 7.23–7.16 (m, 1H),6.93 (d, J = 2.4 Hz, 4H), 6.90 (t, J = 2.4 Hz, 2H), 3.00–2.92 (m, 4H), 2.19(s, 12H), 1.49–1.43 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 153.9, 153.7, 150.0,143.7, 142.1, 140.4, 138.0, 137.0, 133.3, 132.3, 131.9, 131.0, 130.9, 130.0,128.9, 128.3, 128.1, 128.0, 125.9, 122.0, 31.6, 31.3, 21.1, 14.7; 31 P NMR (162MHz, CDCl3) δ 31.34 (s), -5.49 (s); HRMS (EI-TOF) m / z Calcd for C 44 H 42 OP2Si [M] + Found: 676.2480; Found: 676.2479.

[0605] Example 115: I-115

[0606]

[0607] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.67–7.60 (m, 4H),7.56–7.49 (m, 3H), 7.49–7.41 (m, 4H), 7.34–7.28 (m, 1H), 7.22–7.17 (m, 1H),7.12–7.08 (m, 2H), 6.92 (d, J = 2.4 Hz, 4H), 3.00–2.84 (m, 8H), 1.49–1.43 (m, 4H), 1.24 (d, J = 6.8 Hz, 24H); 13 C NMR (100 MHz, CDCl3) δ 153.9, 153.7,151.9, 150.0, 143.7, 142.1, 138.0, 137.5, 133.3, 132.3, 131.9, 130.0, 128.9,128.4, 128.3, 128.1, 128.0, 125.9, 125.2, 122.0, 33.7, 31.6, 31.3, 23.7,14.7; 31 P NMR (162 MHz, CDCl3) δ 31.49 (s), -5.68 (s); HRMS (EI-TOF) m / z Calcdfor C 52 H 58 OP2Si [M] + 788.3732 found: 788.3730.

[0608] Example 116: I-116

[0609]

[0610] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.67–7.60 (m, 4H),7.56–7.49 (m, 3H), 7.49–7.41 (m, 4H), 7.34–7.28 (m, 1H), 7.22–7.17 (m, 1H),7.12–7.08 (m, 2H), 6.92 (d, J = 2.4 Hz, 4H), 3.00–2.84 (m, 8H), 1.49–1.43 (m, 4H), 1.24 (d, J = 6.8 Hz, 24H); 13 C NMR (100 MHz, CDCl3) δ 153.9, 153.7,151.9, 150.0, 143.7, 142.1, 138.0, 137.5, 133.3, 132.3, 131.9, 130.0, 128.9,128.4, 128.3, 128.1, 128.0, 125.9, 125.2, 122.0, 33.7, 31.6, 31.3, 23.7,14.7; 31 P NMR (162 MHz, CDCl3) δ 31.49 (s), -5.68 (s); HRMS (EI-TOF) m / z Calcdfor C 52 H 58 OP2Si [M] + 788.3732 found: 788.3734.

[0611] Example 117: I-117

[0612]

[0613] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.66–7.61 (m, 4H),7.57–7.49 (m, 3H), 7.48–7.43 (m, 4H), 7.34 (t, J = 2.4 Hz, 2H), 7.33–7.30 (m,1H), 7.22–7.17 (m, 1H), 7.16 (d, J = 2.0 Hz, 4H), 3.00–2.92 (m, 4H), 1.49–1.43 (m, 4H), 1.36 (s, 36H); 13 C NMR (100 MHz, CDCl3) δ 153.7, 137.2, 133.3,132.3, 131.9, 130.0, 128.89, 128.87, 128.3, 128.1, 128.0, 125.9, 124.0,122.0, 35.0, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 31.50 (s), -5.12(s); HRMS (EI-TOF) m / z Calcd for C 56 H 66 OP2Si [M] + 844.4358 found: 844.4360.

[0614] Example 118: I-118

[0615]

[0616] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.66–7.61 (m, 4H),7.57–7.49 (m, 3H), 7.48–7.43 (m, 4H), 7.34 (t, J = 2.4 Hz, 2H), 7.33–7.30 (m,1H), 7.22–7.17 (m, 1H), 7.16 (d, J = 2.0 Hz, 4H), 3.00–2.92 (m, 4H), 1.49–1.43 (m, 4H), 1.36 (s, 36H); 13 C NMR (100 MHz, CDCl3) δ 153.7, 137.2, 133.3,132.3, 131.9, 130.0, 128.89, 128.87, 128.3, 128.1, 128.0, 125.9, 124.0,122.0, 35.0, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 31.50 (s), -5.12(s); HRMS (EI-TOF) m / z Calcd for C 56 H 66 OP2Si [M] + 844.4358 found: 844.4356.

[0617] Example 119: I-119

[0618]

[0619] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.79–7.74 (m, 6H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H),7.67–7.60 (m, 4H), 7.56–7.49 (m, 3H), 7.49–7.42 (m, 4H), 7.34–7.29 (m, 1H),7.22–7.16 (m, 1H), 3.00–2.92 (m, 4H), 1.49–1.43 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 153.9, 153.7, 150.1, 143.7, 142.1, 139.1, 138.0, 133.6, 133.3,132.3, 131.9, 130.0, 129.3, 128.9, 128.3, 128.1 128.0, 125.9, 124.6, 123.6,122.0, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.25 (s), -4.30 (s); HRMS(EI-TOF) m / z Calcd for C 44 H 30 F 12 OP2Si [M] + Found: 892.1350; Found: 892.1347.

[0620] Example 120: I-120

[0621]

[0622] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.79–7.74 (m, 6H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H),7.67–7.60 (m, 4H), 7.56–7.49 (m, 3H), 7.49–7.42 (m, 4H), 7.34–7.29 (m, 1H),7.22–7.16 (m, 1H), 3.00–2.92 (m, 4H), 1.49–1.43 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 153.9, 153.7, 150.1, 143.7, 142.1, 139.1, 138.0, 133.6, 133.3,132.3, 131.9, 130.0, 129.3, 128.9, 128.3, 128.1 128.0, 125.9, 124.6, 123.6,122.0, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.25 (s), -4.30 (s); HRMS(EI-TOF) m / z Calcd for C 44 H 30 F 12 OP2Si [M] + 892.1350 found: 892.1351.

[0623] Example 121: I-121

[0624]

[0625] White solid 1H NMR (400 MHz, CDCl3) δ 7.59–7.51 (m, 2H), 7.51–7.44 (m,2H), 7.40 (td, J = 7.6, 2.8 Hz, 2H), 7.32–7.17 (m, 4H), 7.12 (td, J = 7.6,2.8 Hz, 2H), 7.08–7.00 (m, 2H), 7.00–6.94 (m, 1H), 6.90 (dd, J = 12.4, 7.2Hz, 1H), 6.35 (d, J = 2.4 Hz, 1H), 6.32–6.23 (m, 3H), 6.12 (dd, J = 8.2, 2.4Hz, 2H), 3.67 (s, 7H), 3.55 (m, 7H), 3.37–3.17 (m, 1H), 3.16–3.02 (m, 1H),1.38–1.27 (m, 1H), 1.09–0.96 (m, 1H), 0.90–0.82 (m, 2H); 13 C NMR (100 MHz,CDCl3) δ 160.4, 160.3, 160.04, 159.95, 157.7, 157.6, 155.0, 154.8, 148.3,147.7, 142.08, 142.05, 141.93, 141.90, 141.7, 141.6, 140.4, 140.3, 139.4,139.3, 137.6, 136.5, 134.3, 133.7, 133.3, 132.7, 131.94, 131.90, 131.85,131.8, 131.31, 131.30, 131.21, 131.20, 130.4, 130.2, 130.1, 129.4, 128.7,128.5, 128.3, 128.2, 127.9, 127.7, 126.9, 111.4, 111.2, 110.8, 110.6, 101.1,99.9, 55.2, 55.1, 32.5, 32.4, 11.5 (d, J = 3.6 Hz), 10.2; 31 P NMR (162 MHz,CDCl3) δ 30.62 (s), -2.11 (s); HRMS (EI-TOF) m / z Calcd for C 44 H 42 O5P2Si [M] +740.2350 found: 740.2345.

[0626] Example 122: I-122

[0627]

[0628] White solid 1 H NMR (400 MHz, CDCl3) δ 7.59–7.51 (m, 2H), 7.51–7.44 (m,2H), 7.40 (td, J = 7.6, 2.8 Hz, 2H), 7.32–7.17 (m, 4H), 7.12 (td, J = 7.6,2.8 Hz, 2H), 7.08–7.00 (m, 2H), 7.00–6.94 (m, 1H), 6.90 (dd, J = 12.4, 7.2Hz, 1H), 6.35 (d, J = 2.4 Hz, 1H), 6.32–6.23 (m, 3H), 6.12 (dd, J = 8.2, 2.4Hz, 2H), 3.67 (s, 7H), 3.55 (m, 7H), 3.37–3.17 (m, 1H), 3.16–3.02 (m, 1H), 1.38–1.27 (m, 1H), 1.09–0.96 (m, 1H), 0.90–0.82 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 160.4, 160.3, 160.04, 159.95, 157.7, 157.6, 155.0, 154.8, 148.3, 147.7, 142.08, 142.05, 141.93, 141.90, 141.7, 141.6, 140.4, 140.3, 139.4,139.3, 137.6, 136.5, 134.3, 133.7, 133.3, 132.7, 131.94, 131.90, 131.85,131.8, 131.31, 131.30, 131.21, 131.20, 130.4, 130.2, 130.1, 129.4, 128.7,128.5, 128.3, 128.2, 127.9, 127.7, 126.9, 111.4, 111.2, 110.8, 110.6, 101.1,99.9, 55.2, 55.1, 32.5, 32.4, 11.5 (d, J = 3.6 Hz), 10.2; 31 P NMR (162 MHz, CDCl3) δ 30.62 (s), -2.11 (s); HRMS (EI-TOF) m / z Calcd for C 44 H 42 O5P2Si [M] + 740.2350 found: 740.2352.

[0629] Example 123: I-123

[0630]

[0631] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.66–7.61 (m, 4H),7.56–7.49 (m, 3H), 7.49–7.42 (m, 4H), 7.34–7.28 (m, 1H), 7.22–7.16 (m, 1H),6.99 (s, 4H), 3.76 (s, 6H), 3.00–2.92 (m, 4H), 2.07 (s, 12H), 1.49–1.43 (m,4H); 13 C NMR (100 MHz, CDCl3) δ 155.6, 153.9, 153.7, 150.2, 143.7, 142.1,138.0, 134.1, 133.3, 133.2, 132.3, 131.9, 131.0, 130.0, 128.9, 128.3, 128.1,128.0, 125.9, 122.0, 59.9, 31.6, 31.3, 16.0, 14.7; 31 P NMR (162 MHz, CDCl3) δ30.17 (s), -5.23 (s); HRMS (EI-TOF) m / z Calcd for C 46 H 46 O3P2Si [M] + 736.2691 found: 736.2695.

[0632] Example 124: I-124

[0633]

[0634] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.66–7.61 (m, 4H),7.56–7.49 (m, 3H), 7.49–7.42 (m, 4H), 7.34–7.28 (m, 1H), 7.22–7.16 (m, 1H),6.99 (s, 4H), 3.76 (s, 6H), 3.00–2.92 (m, 4H), 2.07 (s, 12H), 1.49–1.43 (m,4H); 13 C NMR (100 MHz, CDCl3) δ 155.6, 153.9, 153.7, 150.2, 143.7, 142.1,138.0, 134.1, 133.3, 133.2, 132.3, 131.9, 131.0, 130.0, 128.9, 128.3, 128.1,128.0, 125.9, 122.0, 59.9, 31.6, 31.3, 16.0, 14.7; 31 P NMR (162 MHz, CDCl3) δ30.17 (s), -5.23 (s); HRMS (EI-TOF) m / z Calcd for C 46 H 46 O3P2Si [M] + 736.2691 found: 736.2693.

[0635] Example 125: I-125

[0636]

[0637] White solid 11H NMR (400 MHz, CDCl3) δ 7.65–7.55 (m, 2H), 7.52–7.44 (m,2H), 7.45–7.36 (m, 2H), 7.32–7.23 (m, 1H), 7.24–7.14 (m, 3H), 7.06–6.92 (m,4H), 6.95–6.86 (m, 4H), 6.83 (d, J = 7.2 Hz, 2H), 3.65 (d, J = 6.0 Hz, 7H),3.59–3.44 (m, 1H), 1.54–1.41 (m, 1H), 1.28 (s, 18H), 1.24 (s, 18H), 1.14–1.03(m, 1H), 1.04–0.83 (m, 2H); 13 13C NMR (100 MHz, CDCl3) δ 159.8, 159.2, 157.9,157.7, 154.5, 154.3, 148.0, 147.4, 142.8, 142.7, 142.28, 142.25, 142.12,142.05, 137.7, 136.6, 134.1, 134.0, 133.5, 133.4, 133.1, 133.0, 132.6, 132.4,132.0, 132.0, 131.9, 131.4, 131.3, 131.23, 131.19, 131.1, 130.4, 130.2,129.4, 129.3, 128.9, 128.8, 128.6, 128.3, 128.1, 128.0, 127.8, 126.4, 64.2,64.1, 35.67, 35.66, 32.5 (d, J = 10.2 Hz), 32.3, 32.1, 32.0, 11.5 (d, J = 3.0Hz), 10.5; 31 31P NMR (162 MHz, CDCl3) δ 30.63 (s), -6.70 (s); HRMS (EI-TOF) m / zCalcd for C 58 H 70 O3P2Si [M] + : 904.4642 found: 904.4641.

[0638] Example 126: I-126

[0639]

[0640] White solid 1 H NMR (400 MHz, CDCl3) δ 7.65–7.55 (m, 2H), 7.52–7.44 (m,2H), 7.45–7.36 (m, 2H), 7.32–7.23 (m, 1H), 7.24–7.14 (m, 3H), 7.06–6.92 (m,4H), 6.95–6.86 (m, 4H), 6.83 (d, J = 7.2 Hz, 2H), 3.65 (d, J = 6.0 Hz, 7H), 3.59–3.44 (m, 1H), 1.54–1.41 (m, 1H), 1.28 (s, 18H), 1.24 (s, 18H), 1.14–1.03(m, 1H), 1.04–0.83 (m, 2H); 13 C NMR (100 MHz, CDCl3) δ 159.8, 159.2, 157.9,157.7, 154.5, 154.3, 148.0, 147.4, 142.8, 142.7, 142.28, 142.25, 142.12,142.05, 137.7, 136.6, 134.1, 134.0, 133.5, 133.4, 133.1, 133.0, 132.6, 132.4,132.0, 132.0, 131.9, 131.4, 131.3, 131.23, 131.19, 131.1, 130.4, 130.2,129.4, 129.3, 128.9, 128.8, 128.6, 128.3, 128.1, 128.0, 127.8, 126.4, 64.2,64.1, 35.67, 35.66, 32.5 (d, J = 10.2 Hz), 32.3, 32.1, 32.0, 11.5 (d, J = 3.0Hz), 10.5; 31 P NMR (162 MHz, CDCl3) δ 30.63 (s), -6.70 (s); HRMS (EI-TOF) m / zCalcd for C 58 H 70 O3P2Si [M] + 904.4642 found: 904.4644.

[0641] Example 127: I-127

[0642]

[0643] White solid 1 H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.81 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.66–7.60 (m, 4H),7.57–7.49 (m, 3H), 7.49–7.42 (m, 4H), 7.36–7.29 (m, 3H), 7.23 (dd, J = 7.6,1.6 Hz, 2H), 7.21–7.14 (m, 3H), 7.10–7.05 (m, 2H), 3.06–2.86 (m, 4H), 2.39(d, J = 0.8 Hz, 6H), 1.49–1.43 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 153.9,153.8, 149.2, 143.7, 142.1, 141.5, 138.0, 136.9, 134.6, 133.3, 132.3, 131.9,130.13, 130.11, 129.0, 128.9, 128.3, 128.1, 128.0, 126.7, 125.9, 122.0, 31.6,31.3, 21.2, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.03 (s), -5.81 (s); HRMS (EI-TOF) m / z Calcd for C 42 H 38 OP2Si [M] + 648.2167 found: 648.2175.

[0644] Example 128: I-128

[0645]

[0646] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.81 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.66–7.60 (m, 4H),7.57–7.49 (m, 3H), 7.49–7.42 (m, 4H), 7.36–7.29 (m, 3H), 7.23 (dd, J = 7.6,1.6 Hz, 2H), 7.21–7.14 (m, 3H), 7.10–7.05 (m, 2H), 3.06–2.86 (m, 4H), 2.39(d, J = 0.8 Hz, 6H), 1.49–1.43 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 153.9,153.8, 149.2, 143.7, 142.1, 141.5, 138.0, 136.9, 134.6, 133.3, 132.3, 131.9,130.13, 130.11, 129.0, 128.9, 128.3, 128.1, 128.0, 126.7, 125.9, 122.0, 31.6,31.3, 21.2, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.03 (s), -5.81 (s); HRMS (EI-TOF) m / z Calcd for C 42 H 38 OP2Si [M] + 648.2167 found: 648.2169.

[0647] Example 129: I-129

[0648]

[0649] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.81 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.66–7.60 (m, 4H),7.56–7.49 (m, 3H), 7.49–7.42 (m, 6H), 7.40 (ddd, J = 8.0, 7.2, 1.2 Hz, 2H),7.34–7.27 (m, 1H), 7.26–7.16 (m, 3H), 7.12–7.07 (m, 2H), 3.23–3.12 (m, 2H), 3.00–2.92 (m, 4H), 1.49–1.43 (m, 4H), 1.18 (d, J = 6.0 Hz, 12H); 13 C NMR (100MHz, CDCl3) δ 153.9, 153.8, 153.5, 150.4, 142.1, 141.6, 138.0, 135.7, 134.8,133.3, 132.3, 131.9, 130.1, 128.9, 128.7, 128.3, 128.2, 128.1, 128.0, 127.62125.9, 122.0, 31.6, 31.3, 30.9, 23.6, 14.7; 31 P NMR (162 MHz, CDCl3) δ 29.98(s), -6.07 (s); HRMS (EI-TOF) m / z Calcd for C 46 H 46 OP2Si [M] + 704.2793 found: 704.2795.

[0650] Example 130: I-130

[0651]

[0652] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.81 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.66–7.60 (m, 4H),7.56–7.49 (m, 3H), 7.49–7.42 (m, 6H), 7.40 (ddd, J = 8.0, 7.2, 1.2 Hz, 2H),7.34–7.27 (m, 1H), 7.26–7.16 (m, 3H), 7.12–7.07 (m, 2H), 3.23–3.12 (m, 2H), 3.00–2.92 (m, 4H), 1.49–1.43 (m, 4H), 1.18 (d, J = 6.0 Hz, 12H); 13 C NMR (100MHz, CDCl3) δ 153.9, 153.8, 153.5, 150.4, 142.1, 141.6, 138.0, 135.7, 134.8,133.3, 132.3, 131.9, 130.1, 128.9, 128.7, 128.3, 128.2, 128.1, 128.0, 127.62125.9, 122.0, 31.6, 31.3, 30.9, 23.6, 14.7; 31 P NMR (162 MHz, CDCl3) δ 29.98(s), -6.07 (s); HRMS (EI-TOF) m / z Calcd for C 46 H 46 OP2Si [M] + 704.2793 found: 704.2797.

[0653] Example 131: I-131

[0654]

[0655] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.81 (dd, J = 7.6, 1.2 Hz, 1H), 7.72–7.66 (m, 3H), 7.66–7.61 (m, 4H), 7.60–7.49 (m, 5H), 7.49–7.38 (m, 8H), 7.34–7.28 (m, 1H), 7.22–7.16 (m, 1H), 3.00–2.92 (m, 4H), 1.69–1.26 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 153.9, 153.8,151.0, 142.1, 141.7, 138.0, 136.3, 135.2, 134.7, 133.3, 132.3, 131.9, 130.2,128.87, 128.85, 128.71, 128.70, 128.3, 128.1, 128.0, 125.9, 125.8, 122.0,31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 29.45 (s), -5.56 (s); 19 F NMR (375MHz, CDCl3) δ -63.35; HRMS (EI-TOF) m / z Calcd for C 42 H 32 F6OP2Si [M] + 756.1602 found: 756.1605.

[0656] Example 132: I-132

[0657]

[0658] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.81 (dd, J = 7.6, 1.2 Hz, 1H), 7.72–7.66 (m, 3H), 7.66–7.61 (m, 4H), 7.60–7.49 (m, 5H), 7.49–7.38 (m, 8H), 7.34–7.28 (m, 1H), 7.22–7.16 (m, 1H), 3.00–2.92 (m, 4H), 1.69–1.26 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 153.9, 153.8,151.0, 142.1, 141.7, 138.0, 136.3, 135.2, 134.7, 133.3, 132.3, 131.9, 130.2,128.87, 128.85, 128.71, 128.70, 128.3, 128.1, 128.0, 125.9, 125.8, 122.0,31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 29.45 (s), -5.56 (s); 19 F NMR (375MHz, CDCl3) δ -63.35; HRMS (EI-TOF) m / z Calcd for C 42 H 32 F6OP2Si [M] + 756.1602 found: 756.1601.

[0659] Example 133: I-133

[0660]

[0661] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.81 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.66–7.60 (m, 4H),7.56–7.49 (m, 3H), 7.49–7.42 (m, 6H), 7.34–7.16 (m, 6H), 6.84 (dd, J = 7.2,1.6 Hz, 2H), 3.78 (s, 6H), 3.09–2.66 (m, 4H), 1.72–1.22 (m, 4H); 13 C NMR (100MHz, CDCl3) δ 165.3, 153.9, 153.8, 150.3, 142.1, 141.6, 138.0, 134.8, 133.3,132.3, 131.9, 130.3, 129.47, 128.9, 128.3, 128.0, 126.6, 125.9, 122.3, 122.0,113.4, 56.1, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 31.68 (s), -5.44(s); HRMS (EI-TOF) m / z Calcd for C 42 H 38 O3P2Si [M] + 680.2065 found: 680.2070.

[0662] Example 134: I-134

[0663]

[0664] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.81 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.66–7.60 (m, 4H),7.56–7.49 (m, 3H), 7.49–7.42 (m, 6H), 7.34–7.16 (m, 6H), 6.84 (dd, J = 7.2,1.6 Hz, 2H), 3.78 (s, 6H), 3.09–2.66 (m, 4H), 1.72–1.22 (m, 4H); 13 C NMR (100MHz, CDCl3) δ 165.3, 153.9, 153.8, 150.3, 142.1, 141.6, 138.0, 134.8, 133.3,132.3, 131.9, 130.3, 129.47, 128.9, 128.3, 128.0, 126.6, 125.9, 122.3, 122.0,113.4, 56.1, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 31.68 (s), -5.44(s); HRMS (EI-TOF) m / z Calcd for C 42 H 38 O3P2Si [M] + 680.2065 found: 680.2066.

[0665] Example 135: I-135

[0666]

[0667] White solid 1H NMR (400 MHz, CDCl3) δ 8.05–7.99 (m, 3H), 7.93 (d, J = 8.0Hz, 2H), 7.89–7.81 (m, 4H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2Hz, 1H), 7.67–7.61 (m, 4H), 7.57–7.48 (m, 7H), 7.48–7.42 (m, 4H), 7.37 (dd, J= 8.0, 2.0 Hz, 2H), 7.33–7.27 (m, 1H), 7.23–7.16 (m, 1H), 3.32–2.62 (m, 4H), 1.84–1.07 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 153.9, 153.7, 150.5, 143.7,142.1, 138.0, 135.7, 134.9, 133.3, 132.9, 132.3, 131.9, 130.7, 130.0, 129.1,128.9, 128.5, 128.3, 128.1, 128.0, 127.76, 127.75, 127.1, 125.9, 122.0, 31.6,31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.23 (s), -6.02 (s); HRMS (EI-TOF) m / zCalcd for C 48 H 38 OP2Si [M] + 720.2167 found: 720.2166.

[0668] Example 136: I-136

[0669]

[0670] White solid 1H NMR (400 MHz, CDCl3) δ 8.05–7.99 (m, 3H), 7.93 (d, J = 8.0Hz, 2H), 7.89–7.81 (m, 4H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2Hz, 1H), 7.67–7.61 (m, 4H), 7.57–7.48 (m, 7H), 7.48–7.42 (m, 4H), 7.37 (dd, J= 8.0, 2.0 Hz, 2H), 7.33–7.27 (m, 1H), 7.23–7.16 (m, 1H), 3.32–2.62 (m, 4H), 1.84–1.07 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 153.9, 153.7, 150.5, 143.7,142.1, 138.0, 135.7, 134.9, 133.3, 132.9, 132.3, 131.9, 130.7, 130.0, 129.1,128.9, 128.5, 128.3, 128.1, 128.0, 127.76, 127.75, 127.1, 125.9, 122.0, 31.6,31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.23 (s), -6.02 (s); HRMS (EI-TOF) m / zCalcd for C 48 H 38 OP2Si [M] + 720.2167 found: 720.2168.

[0671] Example 137: I-137

[0672]

[0673] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.66–7.59 (m, 4H),7.57–7.49 (m, 3H), 7.49–7.42 (m, 4H), 7.35–7.27 (m, 1H), 7.22–7.14 (m, 1H),7.03 (d, J = 2.0 Hz, 2H), 6.91 (dd, J = 9.6, 2.0 Hz, 2H), 6.84 (d, J = 9.6Hz, 2H), 5.99 (s, 4H), 3.00–2.92 (m, 4H), 1.49–1.43 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 153.9, 153.8, 150.3, 149.8, 147.4, 143.8, 142.1, 138.0, 133.3, 132.3, 132.1, 131.9, 130.0, 129.5, 129.0, 128.3, 128.1, 128.0, 125.9, 122.0,113.6, 110.7, 101.4, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 31.56 (s), -6.17 (s); HRMS (EI-TOF) m / z Calcd for C 42 H 34 O5P2Si [M] + 708.1651 found:708.1652.

[0674] Example 138: I-138

[0675]

[0676] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.66–7.59 (m, 4H),7.57–7.49 (m, 3H), 7.49–7.42 (m, 4H), 7.35–7.27 (m, 1H), 7.22–7.14 (m, 1H),7.03 (d, J = 2.0 Hz, 2H), 6.91 (dd, J = 9.6, 2.0 Hz, 2H), 6.84 (d, J = 9.6Hz, 2H), 5.99 (s, 4H), 3.00–2.92 (m, 4H), 1.49–1.43 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 153.9, 153.8, 150.3, 149.8, 147.4, 143.8, 142.1, 138.0, 133.3, 132.3, 132.1, 131.9, 130.0, 129.5, 129.0, 128.3, 128.1, 128.0, 125.9, 122.0,113.6, 110.7, 101.4, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 31.56 (s), -6.17 (s); HRMS (EI-TOF) m / z Calcd for C 42 H 34 O5P2Si [M] + 708.1651 found: 708.1650.

[0677] Example 139: I-139

[0678]

[0679] White solid 1H NMR (400 MHz, CDCl3) δ 8.05–7.99 (m, 2H), 7.69 (t, J = 7.2Hz, 1H), 7.67–7.61 (m, 6H), 7.57–7.39 (m, 12H), 7.38–7.27 (m, 5H), 7.22–7.16(m, 1H), 3.26–2.69 (m, 4H), 1.83–1.11 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ156.1, 154.1, 153.9, 150.8, 146.7, 142.1, 140.8, 138.0, 133.3, 132.3, 131.9,129.7, 129.0, 128.9, 128.3, 128.1, 128.0, 127.0, 125.9, 125.0, 122.5, 122.1,112.5, 112.0, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.91 (s), -5.71(s); HRMS (EI-TOF) m / z Calcd for C 44 H 34 O3P2Si [M] + 700.1752 found: 700.1750.

[0680] Example 140: I-140

[0681]

[0682] White solid 1 H NMR (400 MHz, CDCl3) δ 8.05–7.99 (m, 2H), 7.69 (t, J = 7.2Hz, 1H), 7.67–7.61 (m, 6H), 7.57–7.39 (m, 12H), 7.38–7.27 (m, 5H), 7.22–7.16(m, 1H), 3.26–2.69 (m, 4H), 1.83–1.11 (m, 4H); 13C NMR (100 MHz, CDCl3) δ156.1, 154.1, 153.9, 150.8, 146.7, 142.1, 140.8, 138.0, 133.3, 132.3, 131.9,129.7, 129.0, 128.9, 128.3, 128.1, 128.0, 127.0, 125.9, 125.0, 122.5, 122.1,112.5, 112.0, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.91 (s), -5.71(s); HRMS (EI-TOF) m / z Calcd for C 44 H 34 O3P2Si [M] + 700.1752 found: 700.1754.

[0683] Example 141: I-141

[0684]

[0685] White solid 1 H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.66–7.61 (m, 4H),7.57–7.49 (m, 3H), 7.49–7.42 (m, 4H), 7.35–7.28 (m, 1H), 7.22–7.16 (m, 1H),6.95–6.88 (m, 4H), 6.84 (d, J = 9.6 Hz, 2H), 4.48–4.14 (m, 8H), 3.00–2.92 (m, 4H), 1.49–1.43 (m, 4H); 13C NMR (100 MHz, CDCl3) δ 153.9, 153.8, 150.2, 146.4,143.8, 143.6, 142.1, 138.0, 133.3, 132.3, 131.9, 131.8, 130.2, 130.0, 128.9,128.3, 128.1, 128.0, 125.9, 122.0, 118.8, 115.4, 64.4, 64.2, 31.6, 31.3,14.7; 31 P NMR (162 MHz, CDCl3) δ 31.35 (s), -6.25 (s); HRMS (EI-TOF) m / z Calcdfor C 44 H 38 O5P2Si [M] + 736.1964 found: 736.1960.

[0686] Example 142: I-142

[0687]

[0688] White solid 1 H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.66–7.61 (m, 4H),7.57–7.49 (m, 3H), 7.49–7.42 (m, 4H), 7.35–7.28 (m, 1H), 7.22–7.16 (m, 1H),6.95–6.88 (m, 4H), 6.84 (d, J = 9.6 Hz, 2H), 4.48–4.14 (m, 8H), 3.00–2.92 (m, 4H), 1.49–1.43 (m, 4H); 13C NMR (100 MHz, CDCl3) δ 153.9, 153.8, 150.2, 146.4,143.8, 143.6, 142.1, 138.0, 133.3, 132.3, 131.9, 131.8, 130.2, 130.0, 128.9,128.3, 128.1, 128.0, 125.9, 122.0, 118.8, 115.4, 64.4, 64.2, 31.6, 31.3,14.7; 31 P NMR (162 MHz, CDCl3) δ 31.35 (s), -6.25 (s); HRMS (EI-TOF) m / z Calcdfor C 44 H 38 O5P2Si [M] + 736.1964 found: 736.1961.

[0689] Example 143: I-143

[0690]

[0691] White solid 1 H NMR (400 MHz, CDCl3) δ 8.24 (dd, J = 7.6, 1.2 Hz, 1H), 7.88 (dd, J = 8.4, 1.2 Hz, 1H), 7.70 (dd, J = 7.6, 7.2 Hz, 1H), 7.54–7.46 (m,1H), 7.34–7.26 (m, 1H), 7.16 (dd, J = 8.4, 7.2 Hz, 1H), 3.00–2.92 (m, 4H), 2.67 (p, J = 6.8 Hz, 2H), 2.49 (p, J = 7.2 Hz, 2H), 1.96–1.85 (m, 4H), 1.85–1.75 (m, 4H), 1.75–1.65 (m, 4H), 1.65–1.29 (m, 32H); 1313C NMR (100 MHz, CDCl3) δ 156.5, 155.5, 154.4, 142.7, 140.6, 139.9, 129.6, 128.3, 126.7, 126.0, 125.4, 122.0, 34.2, 31.6, 31.3, 31.1, 29.8, 29.5, 27.0, 26.8, 26.5, 26.0, 14.7; 31 31P NMR (162 MHz, CDCl3) δ 46.24 (s), -2.44 (s); HRMS (EI-TOF) m / z Calcd for C 40 H 58 OP2Si [M] + : 644.3732 found: 644.3737.

[0692] Example 144: I-144

[0693]

[0694] White solid, 1 1H NMR (400 MHz, CDCl3) δ 8.24 (dd, J = 7.6, 1.2 Hz, 1H), 7.88 (dd, J = 8.4, 1.2 Hz, 1H), 7.70 (dd, J = 7.6, 7.2 Hz, 1H), 7.54–7.46 (m, 1H), 7.34–7.26 (m, 1H), 7.16 (dd, J = 8.4, 7.2 Hz, 1H), 3.00–2.92 (m, 4H), 2.67 (p, J = 6.8 Hz, 2H), 2.49 (p, J = 7.2 Hz, 2H), 1.96–1.85 (m, 4H), 1.85–1.75 (m, 4H), 1.75–1.65 (m, 4H), 1.65–1.29 (m, 32H); 13 13C NMR (100 MHz, CDCl3) δ 156.5, 155.5, 154.4, 142.7, 140.6, 139.9, 129.6, 128.3, 126.7, 126.0, 125.4, 122.0, 34.2, 31.6, 31.3, 31.1, 29.8, 29.5, 27.0, 26.8, 26.5, 26.0, 14.7; 31P NMR (162 MHz, CDCl3) δ 46.24 (s), -2.44 (s); HRMS (EI-TOF) m / z Calcdfor C 40 H 58 OP2Si [M] + Found: 644.3732

[0695] Example 145: I-145

[0696]

[0697] White solid 1 H NMR (400 MHz, CDCl3) δ 7.81 (dd, J = 5.6, 1.2 Hz, 1H), 7.74 (dd, J = 7.2, 5.6 Hz, 1H), 7.54–7.48 (m, 2H), 7.34–7.30 (m, 1H), 7.26 (dd, J = 7.2, 6.0 Hz, 1H), 3.13–2.86 (m, 4H), 1.52–1.39 (m, 4H), 1.27 (s,18H), 1.15 (s, 18H); 13 C NMR (100 MHz, CDCl3) δ 158.0, 155.0, 149.9, 146.5,136.3, 133.3, 131.2, 129.4, 129.3, 129.2, 126.0, 122.0, 42.0, 31.6, 31.3,29.9, 29.4, 26.5, 14.6; 31 P NMR (162 MHz, CDCl3) δ 54.66 (s), -4.31 (s); HRMS(EI-TOF) m / z Calcd for C 32 H 50 OP2Si [M] + : 540.3106 found: 540.3112.

[0698] Example 146: I-146

[0699]

[0700] White solid 11H NMR (400 MHz, CDCl3) δ 7.81 (dd, J = 5.6, 1.2 Hz, 1H), 7.74 (dd, J = 7.2, 5.6 Hz, 1H), 7.54–7.48 (m, 2H), 7.34–7.30 (m, 1H), 7.26 (dd, J = 7.2, 6.0 Hz, 1H), 3.13–2.86 (m, 4H), 1.52–1.39 (m, 4H), 1.27 (s, 18H), 1.15 (s, 18H); 13 13C NMR (100 MHz, CDCl3) δ 158.0, 155.0, 149.9, 146.5, 136.3, 133.3, 131.2, 129.4, 129.3, 129.2, 126.0, 122.0, 42.0, 31.6, 31.3, 29.9, 29.4, 26.5, 14.6; 31 31P NMR (162 MHz, CDCl3) δ 54.66 (s), -4.31 (s); HRMS (EI-TOF) m / z Calcd for C 32 11 50 6OP2Si [M] + : 540.3106 found: 540.3108.

[0701] Example 147: I-147

[0702]

[0703] White solid, 1 1H NMR (400 MHz, CDCl3) δ 8.22 (dd, J = 7.6, 1.2 Hz, 1H), 7.83 (dd, J = 8.4, 1.2 Hz, 1H), 7.70 (t, J = 7.2 Hz, 1H), 7.54–7.48 (m, 1H), 7.35–7.29 (m, 1H), 7.16 (dd, J = 8.4, 7.2 Hz, 1H), 3.00–2.92 (m, 4H), 2.86–2.74 (m, 2H), 2.15–2.04 (m, 2H), 1.50–1.43 (m, 4H), 1.16 (d, J = 7.2 Hz, 12H), 1.02 (d, J = 7.2 Hz, 12H); 1313C NMR (100 MHz, CDCl3) δ 156.5, 155.1, 150.5, 143.5, 138.3, 136.0, 130.8, 129.6, 127.4, 126.7, 126.0, 122.0, 31.6, 31.6, 31.3, 25.1, 20.2, 17.0, 14.7; 31 31P NMR (162 MHz, CDCl3) δ 51.48 (s), -3.99 (s); HRMS (EI-TOF) m / z Calcd for C 28 H 42 OP2Si [M] + : 484.2480 found: 484.2483.

[0704] Example 148: I-148

[0705]

[0706] White solid, 1 1H NMR (400 MHz, CDCl3) δ 8.22 (dd, J = 7.6, 1.2 Hz, 1H), 7.83 (dd, J = 8.4, 1.2 Hz, 1H), 7.70 (t, J = 7.2 Hz, 1H), 7.54–7.48 (m, 1H), 7.35–7.29 (m, 1H), 7.16 (dd, J = 8.4, 7.2 Hz, 1H), 3.00–2.92 (m, 4H), 2.86–2.74 (m, 2H), 2.15–2.04 (m, 2H), 1.50–1.43 (m, 4H), 1.16 (d, J = 7.2 Hz, 12H), 1.02 (d, J = 7.2 Hz, 12H); 13 13C NMR (1 hundred MHz, CDCl3) δ 156.5, 155.1, 150.5, 143.5, 138.3, 136.0, 130.8, 129.6, 127.4, 126.7, 126.0, 122.0, 31.6, 31.6, 31.3, 25.1, 20.2, 17.0, 14.7; 31 31P NMR (162 MHz, CDCl3) δ 51.48 (s), -3.99 (s); HRMS (EI-TOF) m / z Calcd for C28 H 42 OP2Si [M] + : 484.2480 found: 484.2481.

[0707] Example 149: I-149

[0708]

[0709] White solid 1 H NMR (400 MHz, CDCl3) δ 8.43 (dd, J = 6.8, 1.2 Hz, 1H), 7.96–7.92 (m, 2H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.66–7.60 (m, 3H), 7.54–7.49 (m, 3H), 7.34–7.29 (m, 1H), 7.23–7.16 (m, 1H), 7.14 (dd, J = 4.0, 1.6Hz, 2H), 6.78–6.74 (m, 2H), 6.57 (dd, J = 3.2, 1.6 Hz, 2H), 3.15–2.76 (m,4H), 1.67–1.21 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 154.3, 153.8, 148.5, 147.1,145.3, 145.1, 143.9, 141.6, 140.9, 136.8, 130.2, 128.9, 128.1, 126.5, 126.0,125.1, 122.0, 117.2, 115.7, 111.4, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3)δ 4.03 (s), -2.30 (s); HRMS (EI-TOF) m / z Calcd for C 32 H 26 O5P2Si [M] + 580.1025 found: 580.1029.

[0710] Example 150: I-150

[0711]

[0712] White solid 1H NMR (400 MHz, CDCl3) δ 8.43 (dd, J = 6.8, 1.2 Hz, 1H), 7.96–7.92 (m, 2H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.66–7.60 (m, 3H), 7.54–7.49 (m, 3H), 7.34–7.29 (m, 1H), 7.23–7.16 (m, 1H), 7.14 (dd, J = 4.0, 1.6Hz, 2H), 6.78–6.74 (m, 2H), 6.57 (dd, J = 3.2, 1.6 Hz, 2H), 3.15–2.76 (m,4H), 1.67–1.21 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 154.3, 153.8, 148.5, 147.1,145.3, 145.1, 143.9, 141.6, 140.9, 136.8, 130.2, 128.9, 128.1, 126.5, 126.0,125.1, 122.0, 117.2, 115.7, 111.4, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3)δ 4.03 (s), -2.30 (s); HRMS (EI-TOF) m / z Calcd for C 32 H 26 O5P2Si [M] + 580.1025 found: 580.1026.

[0713] Example 151: I-151

[0714]

[0715] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.64–7.57 (m, 4H),7.53–7.48 (m, 1H), 7.33–7.30 (m, 1H), 7.26–7.15 (m, 9H), 7.11–7.05 (m, 4H),3.00–2.92 (m, 4H), 2.43–2.39 (m, 12H), 1.49–1.43 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 153.9, 153.7, 151.6, 143.6, 142.2, 141.5, 138.7, 138.0, 135.2, 135.0, 132.9, 130.0, 129.9, 129.8, 129.0, 128.9, 128.1, 128.0, 125.9, 122.0,31.6, 31.3, 21.27, 21.26, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.51 (s), -6.11(s); HRMS (EI-TOF) m / z Calcd for C 44 H 42 OP2Si [M] + : 676.2480 found: 676.2481.

[0716] Example 152: I-152

[0717]

[0718] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.64–7.57 (m, 4H),7.53–7.48 (m, 1H), 7.33–7.30 (m, 1H), 7.26–7.15 (m, 9H), 7.11–7.05 (m, 4H),3.00–2.92 (m, 4H), 2.43–2.39 (m, 12H), 1.49–1.43 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 153.9, 153.7, 151.6, 143.6, 142.2, 141.5, 138.7, 138.0, 135.2, 135.0, 132.9, 130.0, 129.9, 129.8, 129.0, 128.9, 128.1, 128.0, 125.9, 122.0,31.6, 31.3, 21.27, 21.26, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.51 (s), -6.11(s); HRMS (EI-TOF) m / z Calcd for C 44 H 42 OP2Si [M] + Found: 676.2480; Found: 676.2478.

[0719] Example 153: I-153

[0720]

[0721] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.67–7.61 (m, 4H),7.53–7.48 (m, 1H), 7.38–7.29 (m, 5H), 7.22–7.17 (m, 1H), 6.99–6.90 (m, 8H),3.83 (s, 12H), 3.09–2.72 (m, 4H), 1.65–1.13 (m, 4H); 13 C NMR (100 MHz, CDCl3)δ 162.5, 160.4, 153.9, 153.7, 151.3, 143.7, 142.3, 138.0, 136.5, 134.3,131.8, 130.0, 128.9, 128.1, 128.0, 125.9, 125.8, 122.0, 115.2, 114.4, 55.3,31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.10 (s), -6.15 (s); HRMS (EI-TOF) m / z Calcd for C 44 H 42 O5P2Si [M] + 740.2277 found: 740.2280.

[0722] Example 154: I-154

[0723]

[0724] White solid 11H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.67–7.61 (m, 4H), 7.53–7.48 (m, 1H), 7.38–7.29 (m, 5H), 7.22–7.17 (m, 1H), 6.99–6.90 (m, 8H), 3.83 (s, 12H), 3.09–2.72 (m, 4H), 1.65–1.13 (m, 4H); 13 13C NMR (100 MHz, CDCl3) δ 162.5, 160.4, 153.9, 153.7, 151.3, 143.7, 142.3, 138.0, 136.5, 134.3, 131.8, 130.0, 128.9, 128.1, 128.0, 125.9, 125.8, 122.0, 115.2, 114.4, 55.3, 31.6, 31.3, 14.7; 31 31P NMR (162 MHz, CDCl3) δ 30.10 (s), -6.15 (s); HRMS (EI-TOF) m / z Calcd for C 44 18 42 34O5P2Si [M]+ + : 740.2277 found: 740.2275.

[0725] Example 155: I-155

[0726]

[0727] White solid, 1 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.75–7.70 (m, 5H), 7.70–7.65 (m, 9H), 7.63–7.56 (m, 8H), 7.54–7.49 (m, 1H), 7.47–7.42 (m, 8H), 7.41–7.36 (m, 8H), 7.33–7.29 (m, 1H), 7.23–7.16 (m, 1H), 3.11–2.69 (m, 4H), 1.65–1.16 (m, 4H); 13C NMR (100 MHz, CDCl3) δ 153.9, 153.7,151.6, 143.6, 143.1, 142.3, 141.0 (d, J = 4.5 Hz), 140.1, 138.0, 137.7,135.3, 133.4, 132.6, 130.0, 129.3, 128.9, 128.3, 128.0 (d, J = 5.2 Hz), 127.8–127.4 (m), 125.9, 122.0, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ30.53 (s), -6.22 (s); HRMS (EI-TOF) m / z Calcd for C 64 H 50 OP2Si [M] + 924.3106 found: 924.3100.

[0728] Example 156: I-156

[0729]

[0730] White solid 1 H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.75–7.70 (m, 5H), 7.70–7.65 (m, 9H), 7.63–7.56 (m, 8H), 7.54–7.49 (m, 1H),7.47–7.42 (m, 8H), 7.41–7.36 (m, 8H), 7.33–7.29 (m, 1H), 7.23–7.16 (m, 1H),3.11–2.69 (m, 4H), 1.65–1.16 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 153.9, 153.7,151.6, 143.6, 143.1, 142.3, 141.0 (d, J = 4.5 Hz), 140.1, 138.0, 137.7,135.3, 133.4, 132.6, 130.0, 129.3, 128.9, 128.3, 128.0 (d, J = 5.2 Hz), 127.8–127.4 (m), 125.9, 122.0, 31.6, 31.3, 14.7;31 P NMR (162 MHz, CDCl3) δ30.53 (s), -6.22 (s); HRMS (EI-TOF) m / z Calcd for C 64 H 50 OP2Si [M] + 924.3106 found: 924.3103.

[0731] Example 157: I-157

[0732]

[0733] White solid 1 H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.71–7.62 (m, 5H), 7.51 (dq, J = 7.2, 1.2 Hz, 1H), 7.34–7.26 (m, 5H), 7.23–7.16 (m, 1H), 6.77–6.71 (m, 4H), 6.71–6.65 (m,4H), 3.01 (s, 24H), 2.99–2.92 (m, 4H), 1.49–1.43 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 153.9, 153.7, 153.6, 151.5, 151.4, 143.6, 142.2, 138.0, 135.9,133.6, 130.00, 129.96, 128.9, 128.1, 128.0, 125.9, 123.8, 122.0, 114.0,113.3, 40.3, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 31.35 (s), -6.47(s); HRMS (EI-TOF) m / z Calcd for C 48 H 54 N4OP2Si [M] + 792.3542 found: 792.3537.

[0734] Example 158: I-158

[0735]

[0736] White solid 1 H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.71–7.62 (m, 5H), 7.51 (dq, J = 7.2, 1.2 Hz, 1H), 7.34–7.26 (m, 5H), 7.23–7.16 (m, 1H), 6.77–6.71 (m, 4H), 6.71–6.65 (m,4H), 3.01 (s, 24H), 2.99–2.92 (m, 4H), 1.49–1.43 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 153.9, 153.7, 153.6, 151.5, 151.4, 143.6, 142.2, 138.0, 135.9,133.6, 130.00, 129.96, 128.9, 128.1, 128.0, 125.9, 123.8, 122.0, 114.0,113.3, 40.3, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 31.35 (s), -6.47(s); HRMS (EI-TOF) m / z Calcd for C 48 H 54 N4OP2Si [M] + 792.3542 found: 792.3545.

[0737] Example 159: I-159

[0738]

[0739] White solid 1 H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.79–7.74 (m, 4H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H),7.24–7.13 (m, 9H), 3.04–2.81 (m, 4H), 1.60–1.01 (m, 4H); 1313C NMR (100 MHz, CDCl3) δ 165.7, 163.4, 153.9, 153.7, 151.4, 143.7, 142.3, 138.0, 136.9, 135.0, 134.2, 130.0, 128.9, 128.4, 128.1, 128.0, 125.9, 122.0, 116.3, 115.5, 31.6, 31.3, 14.7; 31 31P NMR (162 MHz, CDCl3) δ 29.03 (s), -5.17 (s); 19 19F NMR (375 MHz, CDCl3) δ -107.79, -108.14; HRMS (EI-TOF) m / z Calcd for C 40 H 30 4FOP2Si [M] + : 692.1477 found: 692.1481.

[0740] Example 160: I-160

[0741]

[0742] White solid, 1 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.79–7.74 (m, 4H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.24–7.13 (m, 9H), 3.04–2.81 (m, 4H), 1.60–1.01 (m, 4H); 13 13C NMR (100 MHz, CDCl3) δ 165.7, 163.4, 153.9, 153.7, 151.4, 143.7, 142.3, 138.0, 136.9, 135.0, 134.2, 130.0, 128.9, 128.4, 128.1, 128.0, 125.9, 122.0, 116.3, 115.5, 31.6, 31.3, 14.7; 31 31P NMR (162 MHz, CDCl3) δ 29.03 (s), -5.17 (s); 19F NMR (375MHz, CDCl3) δ -107.79, -108.14; HRMS (EI-TOF) m / z Calcd for C 40 H 30 F4OP2Si [M] + 692.1477 found: 692.1480.

[0743] Example 161: I-161

[0744]

[0745] White solid 1 H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.75–7.66 (m, 6H), 7.54–7.48 (m, 1H), 7.46–7.37 (m, 12H), 7.34–7.29 (m, 1H),7.23–7.16 (m, 1H), 3.11–2.71 (m, 4H), 1.81–1.01 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 153.9, 153.7, 151.5, 143.6, 142.2, 138.0, 137.6, 136.6, 136.3, 135.2, 134.3, 131.0, 130.0, 129.5, 128.9, 128.3, 128.1, 128.0, 125.9, 122.0,31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 29.24 (s), -5.31 (s); HRMS (EI-TOF) m / z Calcd for C 40 H 30 Cl4OP2Si [M] + 756.0295 found: 756.0300.

[0746] Example 162: I-162

[0747]

[0748] White solid 11H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.75–7.66 (m, 6H), 7.54–7.48 (m, 1H), 7.46–7.37 (m, 12H), 7.34–7.29 (m, 1H), 7.23–7.16 (m, 1H), 3.11–2.71 (m, 4H), 1.81–1.01 (m, 4H); 13 13C NMR (100 MHz, CDCl3) δ 153.9, 153.7, 151.5, 143.6, 142.2, 138.0, 137.6, 136.6, 136.3, 135.2, 134.3, 131.0, 130.0, 129.5, 128.9, 128.3, 128.1, 128.0, 125.9, 122.0, 31.6, 31.3, 14.7; 31 31P NMR (162 MHz, CDCl3) δ 29.24 (s), -5.31 (s); HRMS (EI-TOF) m / z Calcd for C 40 11 30 14Cl4OP2Si [M] + : 756.0295 found: 756.0302.

[0749] Example 163: I-163

[0750]

[0751] White solid, 1 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.87–7.80 (m, 4H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.65–7.58 (m, 8H), 7.54–7.48 (m, 5H), 7.34–7.29 (m, 1H), 7.23–7.16 (m, 1H), 3.21–2.65 (m, 4H), 1.77–1.07 (m, 4H); 1313C NMR (100 MHz, CDCl3) δ 153.9, 153.7, 151.6, 143.6, 142.4, 138.0, 137.0, 135.5, 133.6, 133.5, 131.8, 131.5, 130.0, 128.9, 128.1, 128.0, 127.1, 126.1, 125.9, 124.0, 122.0, 31.6, 31.3, 14.7; 31 31P NMR (162 MHz, CDCl3) δ 29.76 (s), -5.89 (s); 19 19F NMR (375 MHz, CDCl3) δ -63.25; HRMS (EI-TOF) m / z Calcd for C 44 H 30 F 12 OP2Si [M] + : 892.1350 found: 892.1357.

[0752] Example 164: I-164

[0753]

[0754] White solid, 1 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.87–7.80 (m, 4H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.65–7.58 (m, 8H), 7.54–7.48 (m, 5H), 7.34–7.29 (m, 1H), 7.23–7.16 (m, 1H), 3.21–2.65 (m, 4H), 1.77–1.07 (m, 4H); 13 13C NMR (100 MHz, CDCl3) δ 153.9, 153.7, 151.6, 143.6, 142.4, 138.0, 137.0, 135.5, 133.6, 133.5, 131.8, 131.5, 130.0, 128.9, 128.1, 128.0, 127.1, 126.1, 125.9, 124.0, 122.0, 31.6, 31.3, 14.7; 31PNMR (162 MHz, CDCl3) δ 29.76 (s), -5.89 (s); 19 F NMR (375 MHz, CDCl3) δ -63.25; HRMS (EI-TOF) m / z Calcd for C 44 H 30 F 12 OP2Si [M] + 892.1350 found: 892.1355.

[0755] Example 165: I-165

[0756]

[0757] White solid 1 H NMR (400 MHz, CDCl3) δ 7.48–7.35 (m, 5H), 7.29–7.20 (m,3H), 7.19–7.09 (m, 6H), 7.09–7.01 (m, 4H), 7.01–6.82 (m, 4H), 3.70–3.53 (m,2H), 3.25–2.94 (m, 2H), 1.64–1.50 (m, 1H), 1.29 (d, J = 8.4 Hz, 18H), 1.19 (d, J = 20.4 Hz, 18H), 1.15–1.05 (m, 1H), 1.05–0.86 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 157.7, 157.6, 155.1, 155.0, 154.5, 154.4, 153.9, 153.8, 150.64,150.63, 147.4, 146.9, 141.83, 141.81, 141.68, 141.66, 141.6, 138.0, 137.0,135.9, 135.7, 134.8, 134.7, 133.6, 133.4, 132.8, 132.6, 131.8, 131.7, 131.6,130.6, 130.5, 130.4, 130.2, 129.5, 129.31, 129.28, 129.1, 128.6, 128.4,126.3, 125.2, 125.1, 125.0, 124.9, 124.80, 124.75, 124.7, 34.9, 34.7, 34.5,34.4, 32.5, 32.3 (d, J = 10.9 Hz), 31.3, 31.2, 31.1, 31.0, 10.9 (d, J = 4.1Hz), 10.7; 31 P NMR (162 MHz, CDCl3) δ 30.69 (s), -8.10 (s); HRMS (EI-TOF) m / zCalcd for C 56 H 66 OP2Si [M] + 844.4431 found: 844.4428.

[0758] Example 166: I-166

[0759]

[0760] White solid 11H NMR (400 MHz, CDCl3) δ 7.48–7.35 (m, 5H), 7.29–7.20 (m, 3H), 7.19–7.09 (m, 6H), 7.09–7.01 (m, 4H), 7.01–6.82 (m, 4H), 3.70–3.53 (m, 2H), 3.25–2.94 (m, 2H), 1.64–1.50 (m, 1H), 1.29 (d, J = 8.4 Hz, 18H), 1.19 (d, J = 20.4 Hz, 18H), 1.15–1.05 (m, 1H), 1.05–0.86 (m, 2H); 13 13C NMR (100 MHz, CDCl3) δ 157.7, 157.6, 155.1, 155.0, 154.5, 154.4, 153.9, 153.8, 150.64, 150.63, 147.4, 146.9, 141.83, 141.81, 141.68, 141.66, 141.6, 138.0, 137.0, 135.9, 135.7, 134.8, 134.7, 133.6, 133.4, 132.8, 132.6, 131.8, 131.7, 131.6, 130.6, 130.5, 130.4, 130.2, 129.5, 129.31, 129.28, 129.1, 128.6, 128.4, 126.3, 125.2, 125.1, 125.0, 124.9, 124.80, 124.75, 124.7, 34.9, 34.7, 34.5, 34.4, 32.5, 32.3 (d, J = 10.9 Hz), 31.3, 31.2, 31.1, 31.0, 10.9 (d, J = 4.1 Hz), 10.7; 31 31P NMR (162 MHz, CDCl3) δ 30.69 (s), -8.10 (s); HRMS (EI-TOF) m / z Calcd for C 56 H 66 OP2Si [M] + : 844.4431 found: 844.4430.

[0761] Example 167: I-167

[0762]

[0763] White solid 1 H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.60–7.53 (m, 4H),7.52–7.48 (m, 1H), 7.37–7.29 (m, 3H), 7.25–7.08 (m, 11H), 3.18–2.83 (m, 4H),2.49–2.20 (m, 12H), 1.59–1.27 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 153.9,153.7, 150.7, 143.6, 141.3, 140.3, 140.1, 138.0, 137.1, 133.1, 132.8, 132.5,131.3, 131.0, 130.0, 129.8, 129.7, 129.0, 128.9, 128.6, 128.1, 128.0, 125.9,122.0, 31.6, 31.3, 21.5, 21.1, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.19 (s), -6.31 (s); HRMS (EI-TOF) m / z Calcd for C 44 H 42 OP2Si [M] + : 676.2480 found:676.2481.

[0764] Example 168: I-168

[0765]

[0766] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.60–7.53 (m, 4H),7.52–7.48 (m, 1H), 7.37–7.29 (m, 3H), 7.25–7.08 (m, 11H), 3.18–2.83 (m, 4H),2.49–2.20 (m, 12H), 1.59–1.27 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 153.9,153.7, 150.7, 143.6, 141.3, 140.3, 140.1, 138.0, 137.1, 133.1, 132.8, 132.5,131.3, 131.0, 130.0, 129.8, 129.7, 129.0, 128.9, 128.6, 128.1, 128.0, 125.9,122.0, 31.6, 31.3, 21.5, 21.1, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.19 (s), -6.31 (s); HRMS (EI-TOF) m / z Calcd for C 44 H 42 OP2Si [M] + : 676.2480 found: 676.2484.

[0767] Example 169: I-169

[0768]

[0769] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.62–7.57 (m, 2H),7.56–7.53 (m, 2H), 7.51 (dq, J = 7.2, 1.2 Hz, 1H), 7.37 (dd, J = 7.6, 6.8 Hz,2H), 7.34–7.26 (m, 3H), 7.24–7.13 (m, 7H), 6.99 (dd, J = 2.4, 1.6 Hz, 2H),3.14–2.64 (m, 8H), 1.66–1.38 (m, 4H), 1.27 (d, J = 6.8 Hz, 24H); 13 C NMR (100MHz, CDCl3) δ 153.9, 153.7, 150.9, 150.7, 150.6, 143.6, 141.5, 138.0, 137.7,133.3, 133.2, 131.5, 130.2, 130.0, 129.2, 129.0, 128.9, 128.8, 128.4, 128.1,128.0, 126.5, 125.9, 122.0, 33.6, 32.8, 31.6, 31.3, 23.9, 14.7; 31 P NMR (162MHz, CDCl3) δ 30.25 (s), -6.32 (s); HRMS (EI-TOF) m / z Calcd for C 52 H 58 OP2Si [M] + 788.3732 found: 788.3733.

[0770] Example 170: I-170

[0771]

[0772] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.62–7.57 (m, 2H),7.56–7.53 (m, 2H), 7.51 (dq, J = 7.2, 1.2 Hz, 1H), 7.37 (dd, J = 7.6, 6.8 Hz,2H), 7.34–7.26 (m, 3H), 7.24–7.13 (m, 7H), 6.99 (dd, J = 2.4, 1.6 Hz, 2H),3.14–2.64 (m, 8H), 1.66–1.38 (m, 4H), 1.27 (d, J = 6.8 Hz, 24H); 13 C NMR (100MHz, CDCl3) δ 153.9, 153.7, 150.9, 150.7, 150.6, 143.6, 141.5, 138.0, 137.7,133.3, 133.2, 131.5, 130.2, 130.0, 129.2, 129.0, 128.9, 128.8, 128.4, 128.1,128.0, 126.5, 125.9, 122.0, 33.6, 32.8, 31.6, 31.3, 23.9, 14.7; 31 P NMR (162MHz, CDCl3) δ 30.25 (s), -6.32 (s); HRMS (EI-TOF) m / z Calcd for C 52 H 58 OP2Si [M] + 788.3732 found: 788.3735.

[0773] Example 171: I-171

[0774]

[0775] White solid 11H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.75–7.66 (m, 4H), 7.64 (dt, J = 5.6, 2.0 Hz, 2H), 7.53–7.48 (m, 1H), 7.39–7.16 (m, 14H), 3.00–2.92 (m, 4H), 1.49–1.43 (m, 4H), 1.34 (d, J = 3.2 Hz, 36H); 13 13C NMR (100 MHz, CDCl3) δ 153.9, 152.9, 137.2, 133.7, 132.9, 132.0, 130.4, 130.0, 129.0, 128.9, 128.8, 128.4, 128.2, 128.1, 128.0, 126.3, 125.9, 122.0, 34.6, 34.6, 31.6, 31.3, 31.3, 14.7; 31 31P NMR (162 MHz, CDCl3) δ 30.37(s), -6.40 (s); HRMS (EI-TOF) m / z Calcd for C 56 1H 66 OP2Si [M] + : 844.4431 found: 844.4435.

[0776] Example 172: I-172

[0777]

[0778] White solid, 1 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.75–7.66 (m, 4H), 7.64 (dt, J = 5.6, 2.0 Hz, 2H), 7.53–7.48 (m, 1H), 7.39–7.16 (m, 14H), 3.00–2.92 (m, 4H), 1.49–1.43 (m, 4H), 1.34 (d, J = 3.2 Hz, 36H); 13C NMR (100 MHz, CDCl3) δ 153.9, 152.9, 137.2, 133.7, 132.9, 132.0,130.4, 130.0, 129.0, 128.9, 128.8, 128.4, 128.2, 128.1, 128.0, 126.3, 125.9,122.0, 34.6, 34.6, 31.6, 31.3, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.37(s), -6.40 (s); HRMS (EI-TOF) m / z Calcd for C 56 H 66 OP2Si [M] + 844.4431 found: 844.4437.

[0779] Example 173: I-173

[0780]

[0781] White solid 1 H NMR (400 MHz, CDCl3) δ 8.05 (t, J = 2.4 Hz, 2H), 8.02 (dd,J = 6.8, 1.2 Hz, 1H), 7.82 (d, J = 2.0 Hz, 2H), 7.76–7.65 (m, 6H), 7.63–7.54(m, 6H), 7.53–7.48 (m, 1H), 7.34–7.29 (m, 1H), 7.28–7.16 (m, 3H), 3.12–2.71(m, 4H), 1.70–1.21 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 153.9, 153.7, 150.5,143.7, 141.3, 137.9, 137.8, 133.67, 133.65, 133.4, 133.2, 132.0, 130.0,129.6, 129.2, 129.0, 128.9, 128.7, 128.3, 128.1, 128.0, 126.5, 125.9, 123.92,123.90, 122.0, 31.6, 31.3, 14.7; 3131P NMR (162 MHz, CDCl3) δ 30.11 (s), -6.06(s); 19 19F NMR (375 MHz, CDCl3) δ -63.35; HRMS (EI-TOF) m / z Calcd forC 44 H 30 F 12 OP2Si [M] + : 892.1350 found: 892.1344.

[0782] Example 174: I-174

[0783]

[0784] White solid, 1 1H NMR (400 MHz, CDCl3) δ 8.05 (t, J = 2.4 Hz, 2H), 8.02 (dd,J = 6.8, 1.2 Hz, 1H), 7.82 (d, J = 2.0 Hz, 2H), 7.76–7.65 (m, 6H), 7.63–7.54(m, 6H), 7.53–7.48 (m, 1H), 7.34–7.29 (m, 1H), 7.28–7.16 (m, 3H), 3.12–2.71(m, 4H), 1.70–1.21 (m, 4H); 13 13C NMR (100 MHz, CDCl3) δ 153.9, 153.7, 150.5,143.7, 141.3, 137.9, 137.8, 133.67, 133.65, 133.4, 133.2, 132.0, 130.0,129.6, 129.2, 129.0, 128.9, 128.7, 128.3, 128.1, 128.0, 126.5, 125.9, 123.92,123.90, 122.0, 31.6, 31.3, 14.7; 31 31P NMR (162 MHz, CDCl3) δ 30.11 (s), -6.06(s); 19 19F NMR (375 MHz, CDCl3) δ -63.35; HRMS (EI-TOF) m / z Calcd forC 44 H 30 F 12 OP2Si [M] +892.1350 found: 892.1351.

[0785] Example 175: I-175

[0786]

[0787] White solid 1 H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.58–7.53 (m, 2H),7.53–7.49 (m, 1H), 7.35–7.28 (m, 5H), 7.26 (t, J = 2.0 Hz, 2H), 7.23–7.16 (m,1H), 7.13–7.08 (m, 2H), 6.96 (t, J = 2.0 Hz, 2H), 6.90–6.82 (m, 4H), 3.82 (s,12H), 3.00–2.92 (m, 4H), 1.56–1.26 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 161.8,161.7, 154.0, 153.8, 150.2, 143.6, 141.2, 138.2, 138.0, 134.3, 130.0, 129.6,129.1, 128.9, 128.1, 128.0, 127.6, 126.0, 125.9, 122.0, 117.8, 117.5, 115.5,114.7, 55.5, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.47 (s), -6.37(s); HRMS (EI-TOF) m / z Calcd for C 44 H 42 O5P2Si [M] + 740.2277 found: 740.2275.

[0788] Example 176: I-176

[0789]

[0790] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.58–7.53 (m, 2H),7.53–7.49 (m, 1H), 7.35–7.28 (m, 5H), 7.26 (t, J = 2.0 Hz, 2H), 7.23–7.16 (m,1H), 7.13–7.08 (m, 2H), 6.96 (t, J = 2.0 Hz, 2H), 6.90–6.82 (m, 4H), 3.82 (s,12H), 3.00–2.92 (m, 4H), 1.56–1.26 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 161.8,161.7, 154.0, 153.8, 150.2, 143.6, 141.2, 138.2, 138.0, 134.3, 130.0, 129.6,129.1, 128.9, 128.1, 128.0, 127.6, 126.0, 125.9, 122.0, 117.8, 117.5, 115.5,114.7, 55.5, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.47 (s), -6.37(s); HRMS (EI-TOF) m / z Calcd for C 44 H 42 O5P2Si [M] + 740.2277 found: 740.2278.

[0791] Example 177: I-177

[0792]

[0793] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.1 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.57 (ddd, J = 7.2,2.4, 1.2 Hz, 2H), 7.54–7.48 (m, 1H), 7.38–7.29 (m, 5H), 7.25 (t, J = 2.4 Hz,2H), 7.22–7.17 (m, 1H), 7.13–7.08 (m, 2H), 6.87–6.81 (m, 4H), 6.81–6.75 (m,2H), 4.79–4.47 (m, 4H), 3.06–2.71 (m, 4H), 1.49–1.43 (m, 4H), 1.33 (d, J =5.6 Hz, 24H); 13 C NMR (100 MHz, CDCl3) δ 160.3, 159.8, 154.0, 153.8, 150.2,143.6, 141.2, 138.3, 138.0, 134.3, 130.0, 129.8, 129.3, 128.9, 128.1, 128.0,127.6, 126.0, 125.9, 122.0, 120.6, 119.7, 118.4, 117.2, 70.12, 70.10, 31.6,31.3, 21.9, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.63 (s), -6.71 (s); HRMS (EI-TOF) m / z Calcd for C 52 H 58 O5P2Si [M] + 852.3529 found: 852.3530.

[0794] Example 178: I-178

[0795]

[0796] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.1 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.57 (ddd, J = 7.2,2.4, 1.2 Hz, 2H), 7.54–7.48 (m, 1H), 7.38–7.29 (m, 5H), 7.25 (t, J = 2.4 Hz,2H), 7.22–7.17 (m, 1H), 7.13–7.08 (m, 2H), 6.87–6.81 (m, 4H), 6.81–6.75 (m,2H), 4.79–4.47 (m, 4H), 3.06–2.71 (m, 4H), 1.49–1.43 (m, 4H), 1.33 (d, J =5.6 Hz, 24H); 13 C NMR (100 MHz, CDCl3) δ 160.3, 159.8, 154.0, 153.8, 150.2,143.6, 141.2, 138.3, 138.0, 134.3, 130.0, 129.8, 129.3, 128.9, 128.1, 128.0,127.6, 126.0, 125.9, 122.0, 120.6, 119.7, 118.4, 117.2, 70.12, 70.10, 31.6,31.3, 21.9, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.63 (s), -6.71 (s); HRMS (EI-TOF) m / z Calcd for C 52 H 58 O5P2Si [M] + 852.3529 found: 852.3534.

[0797] Example 179: I-179

[0798]

[0799] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.60–7.54 (m, 2H),7.54–7.48 (m, 1H), 7.45–7.39 (m, 8H), 7.39–7.24 (m, 19H), 7.22–7.16 (m, 1H),7.13–7.08 (m, 2H), 7.03–6.98 (m, 2H), 6.97–6.93 (m, 2H), 6.92 (t, J = 2.0 Hz,2H), 5.07 (t, J = 1.2 Hz, 8H), 3.20–2.82 (m, 4H), 1.81–0.97 (m, 4H); 13 C NMR(100 MHz, CDCl3) δ 160.8, 160.6, 154.0, 153.8, 150.2, 143.6, 141.2, 138.1,138.0, 136.9, 134.2, 130.9, 130.0, 129.6, 129.2, 128.9, 128.6, 128.4, 128.1,128.0, 127.6, 126.0, 125.9, 122.0, 119.3, 118.9, 117.1, 116.2, 70.0, 31.6,31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.60 (s), -6.73 (s); HRMS (EI-TOF) m / zCalcd for C 68 H 58 O5P2Si [M] + : 1044.3529 found: 1044.3530.

[0800] Example 180: I-180

[0801]

[0802] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.60–7.54 (m, 2H),7.54–7.48 (m, 1H), 7.45–7.39 (m, 8H), 7.39–7.24 (m, 19H), 7.22–7.16 (m, 1H),7.13–7.08 (m, 2H), 7.03–6.98 (m, 2H), 6.97–6.93 (m, 2H), 6.92 (t, J = 2.0 Hz,2H), 5.07 (t, J = 1.2 Hz, 8H), 3.20–2.82 (m, 4H), 1.81–0.97 (m, 4H); 13 C NMR(100 MHz, CDCl3) δ 160.8, 160.6, 154.0, 153.8, 150.2, 143.6, 141.2, 138.1,138.0, 136.9, 134.2, 130.9, 130.0, 129.6, 129.2, 128.9, 128.6, 128.4, 128.1,128.0, 127.6, 126.0, 125.9, 122.0, 119.3, 118.9, 117.1, 116.2, 70.0, 31.6,31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.60 (s), -6.73 (s); HRMS (EI-TOF) m / zCalcd for C 68 H 58 O5P2Si [M] + : 1044.3529 found: 1044.3531.

[0803] Example 181: I-181

[0804]

[0805] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.62–7.56 (m, 2H),7.54–7.48 (m, 3H), 7.43–7.34 (m, 4H), 7.34–7.29 (m, 1H), 7.28–7.22 (m, 4H),7.21–7.17 (m, 1H), 7.17–7.13 (m, 2H), 7.13–7.08 (m, 2H), 3.00–2.92 (m, 4H), 1.49–1.43 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 154.0, 153.8, 152.3, 151.7,150.4, 143.6, 141.2, 138.1, 138.0, 134.4, 130.0, 129.7, 129.3, 128.9, 128.1,128.0, 127.6, 126.0, 125.9, 125.2, 124.6, 122.6, 122.0, 121.5, 120.4, 31.6,31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.26 (s), -6.18 (s); 19 F NMR (375 MHz, CDCl3) δ -58.24; HRMS (EI-TOF) m / z Calcd for C 44 H 30 F 12 O5P2Si [M] + 956.1146 found: 956.1150.

[0806] Example 182: I-182

[0807]

[0808] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.62–7.56 (m, 2H),7.54–7.48 (m, 3H), 7.43–7.34 (m, 4H), 7.34–7.29 (m, 1H), 7.28–7.22 (m, 4H),7.21–7.17 (m, 1H), 7.17–7.13 (m, 2H), 7.13–7.08 (m, 2H), 3.00–2.92 (m, 4H), 1.49–1.43 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 154.0, 153.8, 152.3, 151.7,150.4, 143.6, 141.2, 138.1, 138.0, 134.4, 130.0, 129.7, 129.3, 128.9, 128.1,128.0, 127.6, 126.0, 125.9, 125.2, 124.6, 122.6, 122.0, 121.5, 120.4, 31.6,31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.26 (s), -6.18 (s); 19 F NMR (375 MHz, CDCl3) δ -58.24; HRMS (EI-TOF) m / z Calcd for C 44 H 30 F 12 O5P2Si [M] + 956.1146 found: 956.1153.

[0809] Example 183: I-183

[0810]

[0811] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H),7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.55–7.49 (m, 1H),7.48 (d, J = 2.0 Hz, 4H), 7.34–7.29 (m, 1H), 7.23–7.16 (m, 1H), 7.02–6.98 (m,2H), 6.93 (d, J = 2.4 Hz, 4H), 6.91–6.87 (m, 2H), 3.00–2.92 (m, 4H), 2.17 (d,J = 18.0 Hz, 24H), 1.71–1.33 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 153.9, 153.7,150.0, 143.7, 141.1, 140.4, 139.1, 138.0, 137.0, 132.5, 132.3, 131.0, 130.9,130.0, 129.3, 128.9, 128.1, 128.0, 125.9, 122.0, 31.6, 31.3, 21.1, 14.7; 31 PNMR (162 MHz, CDCl3) δ 29.94 (s), -6.03 (s); HRMS (EI-TOF) m / z Calcd forC 48 H 50 OP2Si [M] + 732.3106 found: 732.3114.

[0812] Example 184: I-184

[0813]

[0814] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H),7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.55–7.49 (m, 1H),7.48 (d, J = 2.0 Hz, 4H), 7.34–7.29 (m, 1H), 7.23–7.16 (m, 1H), 7.02–6.98 (m,2H), 6.93 (d, J = 2.4 Hz, 4H), 6.91–6.87 (m, 2H), 3.00–2.92 (m, 4H), 2.17 (d,J = 18.0 Hz, 24H), 1.71–1.33 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 153.9, 153.7,150.0, 143.7, 141.1, 140.4, 139.1, 138.0, 137.0, 132.5, 132.3, 131.0, 130.9,130.0, 129.3, 128.9, 128.1, 128.0, 125.9, 122.0, 31.6, 31.3, 21.1, 14.7; 31 PNMR (162 MHz, CDCl3) δ 29.94 (s), -6.03 (s); HRMS (EI-TOF) m / z Calcd forC 48 H 50 OP2Si [M] + 732.3106 found: 732.3108.

[0815] Example 185: I-185

[0816]

[0817] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H),7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.53–7.48 (m, 1H),7.46 (d, J = 2.0 Hz, 4H), 7.33–7.30 (m, 1H), 7.23–7.16 (m, 3H), 7.12–7.08 (m,2H), 6.92 (d, J = 2.4 Hz, 4H), 3.15–2.68 (m, 12H), 1.71–1.36 (m, 4H), 1.36–0.92 (m, 48H); 13 C NMR (100 MHz, CDCl3) δ 151.9, 151.5, 137.5, 132.2, 130.0,128.9, 128.4, 128.1, 128.0, 127.4, 126.8, 125.9, 125.2, 122.0, 34.6, 33.7,31.6, 31.3, 23.7, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.07 (s), -6.12 (s); HRMS(EI-TOF) m / z Calcd for C 64 H 82 OP2Si [M] + 956.5610 found: 956.5604.

[0818] Example 186: I-186

[0819]

[0820] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H),7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.53–7.48 (m, 1H),7.46 (d, J = 2.0 Hz, 4H), 7.33–7.30 (m, 1H), 7.23–7.16 (m, 3H), 7.12–7.08 (m,2H), 6.92 (d, J = 2.4 Hz, 4H), 3.15–2.68 (m, 12H), 1.71–1.36 (m, 4H), 1.36–0.92 (m, 48H); 13 C NMR (100 MHz, CDCl3) δ 151.9, 151.5, 137.5, 132.2, 130.0,128.9, 128.4, 128.1, 128.0, 127.4, 126.8, 125.9, 125.2, 122.0, 34.6, 33.7,31.6, 31.3, 23.7, 14.7; 31 P NMR (162 MHz, CDCl3) δ 30.07 (s), -6.12 (s); HRMS(EI-TOF) m / z Calcd for C 64 H 82 OP2Si [M] + 956.5610 found: 956.5612.

[0821] Example 187: I-187

[0822]

[0823] White solid 11H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.63 (d, J = 2.0 Hz, 4H), 7.54–7.48 (m, 1H), 7.36–7.29 (m, 5H), 7.22–7.17 (m, 1H), 7.16 (d, J = 2.4 Hz, 4H), 3.33–2.64 (m, 4H), 1.56–1.41 (m, 4H), 1.36 (s, 72H); 13 13C NMR(100 MHz, CDCl3) δ 153.7, 153.2, 128.9, 127.4, 125.3, 124.0, 34.97, 34.95, 31.6, 31.3, 14.7; 31 31P NMR (162 MHz, CDCl3) δ 30.21 (s), -6.19 (s); HRMS (EI-TOF) m / z Calcd for C 72 H 98 OP2Si [M] + : 1068.6862 found: 1068.6865.

[0824] Example 188: I-188

[0825]

[0826] White solid, 1 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.63 (d, J = 2.0 Hz, 4H), 7.54–7.48 (m, 1H), 7.36–7.29 (m, 5H), 7.22–7.17 (m, 1H), 7.16 (d, J = 2.4 Hz, 4H), 3.33–2.64 (m, 4H), 1.56–1.41 (m, 4H), 1.36 (s, 72H); 1313C NMR (100 MHz, CDCl3) δ 153.7, 153.2, 128.9, 127.4, 125.3, 124.0, 34.97, 34.95, 31.6, 31.3, 14.7; 31 31P NMR (162 MHz, CDCl3) δ 30.21 (s), -6.19 (s); HRMS (EI-TOF) m / z Calcd for C 72 H 98 OP2Si [M] + : 1068.6862 found: 1068.6868.

[0827] Example 189: I-189

[0828]

[0829] White solid, 1 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.91 (d, J = 2.4 Hz, 4H), 7.84 (t, J = 2.4 Hz, 2H), 7.78–7.74 (m, 6H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.54–7.48 (m, 1H), 7.34–7.29 (m, 1H), 7.23–7.16 (m, 1H), 3.00–2.92 (m, 4H), 1.54–1.26 (m, 4H); 13 13C NMR(100 MHz, CDCl3) δ 153.9, 153.7, 150.1, 143.7, 141.0, 139.1, 137.9, 134.8, 134.0, 133.6, 130.0, 129.3, 128.9, 128.1, 128.03, 127.97, 126.2, 125.9, 124.6, 123.59, 123.57, 122.0, 31.6, 31.3, 14.7; 31 31P NMR (162 MHz, CDCl3) δ 30.03 (s), -5.97 (s); HRMS (EI-TOF) m / z Calcd for C 48 H 26 F 24OP2Si [M] + 1164.0845 found: 1164.0849.

[0830] Example 190: I-190

[0831]

[0832] White solid 1 H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.91 (d, J = 2.4 Hz, 4H), 7.84 (t, J = 2.4 Hz, 2H), 7.78–7.74 (m, 6H), 7.72(dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.54–7.48 (m, 1H), 7.34–7.29 (m, 1H), 7.23–7.16 (m, 1H), 3.00–2.92 (m, 4H), 1.54–1.26 (m, 4H); 13 C NMR(100 MHz, CDCl3) δ 153.9, 153.7, 150.1, 143.7, 141.0, 139.1, 137.9, 134.8,134.0, 133.6, 130.0, 129.3, 128.9, 128.1, 128.03, 127.97, 126.2, 125.9,124.6, 123.59, 123.57, 122.0, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ30.03 (s), -5.97 (s); HRMS (EI-TOF) m / z Calcd for C 48 H 26 F 24 OP2Si [M] + 1164.0845 found: 1164.0850.

[0833] Example 191: I-191

[0834]

[0835] White solid 1H NMR (400 MHz, CDCl3) δ 7.44 (d, J = 8.0 Hz, 1H), 7.33–7.23(m, 1H), 7.19 (q, J = 7.6 Hz, 1H), 7.07 (dd, J = 12.8, 7.2 Hz, 1H), 6.93 (d,J = 5.6 Hz, 1H), 6.69 (d, J = 12.8 Hz, 1H), 6.54 (s, 1H), 6.45 (d, J = 13.2Hz, 2H), 6.35 (d, J = 6.8 Hz, 2H), 6.29 (dd, J = 7.6, 2.4 Hz, 2H), 6.25 (s,1H), 6.11 (dd, J = 8.0, 2.0 Hz, 2H), 3.70 (d, J = 27.6 Hz, 12H), 3.64–3.40(m, 14H), 3.26–2.99 (m, 2H), 1.50–1.37 (m, 1H), 1.09–0.77 (m, 2H); 13 C NMR(100 MHz, CDCl3) δ 160.6, 160.41, 160.36, 160.3, 160.2, 160.03, 160.00,159.9, 157.6, 157.5, 154.8, 154.7, 147.7, 147.2, 141.81, 141.78, 141.7,141.6, 141.4, 141.2, 140.4, 140.3, 139.9, 139.8, 136.9, 136.6, 135.9, 135.6,135.1, 134.1, 130.5, 130.3, 129.52, 129.49, 129.3, 128.6, 128.5, 126.7,111.5, 111.3, 111.1, 110.9, 109.9, 109.8, 109.6, 109.5, 103.54, 103.52,103.19, 103.17, 100.4, 100.1, 55.4, 55.2, 55.1, 55. 0, 32.4, 32.2 (d, J = 9.3Hz), 10.9 (d, J = 3.0 Hz), 10.5; 31 P NMR (162 MHz, CDCl3) δ 31.55 (s), -1.97(s); HRMS (EI-TOF) m / z Calcd for C48 H 50 O9P2Si [M] + 860.2772 found: 860.2767.

[0836] Example 192: I-192

[0837]

[0838] White solid 1 H NMR (400 MHz, CDCl3) δ 7.44 (d, J = 8.0 Hz, 1H), 7.33–7.23(m, 1H), 7.19 (q, J = 7.6 Hz, 1H), 7.07 (dd, J = 12.8, 7.2 Hz, 1H), 6.93 (d,J = 5.6 Hz, 1H), 6.69 (d, J = 12.8 Hz, 1H), 6.54 (s, 1H), 6.45 (d, J = 13.2Hz, 2H), 6.35 (d, J = 6.8 Hz, 2H), 6.29 (dd, J = 7.6, 2.4 Hz, 2H), 6.25 (s,1H), 6.11 (dd, J = 8.0, 2.0 Hz, 2H), 3.70 (d, J = 27.6 Hz, 12H), 3.64–3.40(m, 14H), 3.26–2.99 (m, 2H), 1.50–1.37 (m, 1H), 1.09–0.77 (m, 2H); 13C NMR(100 MHz, CDCl3) δ 160.6, 160.41, 160.36, 160.3, 160.2, 160.03, 160.00,159.9, 157.6, 157.5, 154.8, 154.7, 147.7, 147.2, 141.81, 141.78, 141.7,141.6, 141.4, 141.2, 140.4, 140.3, 139.9, 139.8, 136.9, 136.6, 135.9, 135.6,135.1, 134.1, 130.5, 130.3, 129.52, 129.49, 129.3, 128.6, 128.5, 126.7,111.5, 111.3, 111.1, 110.9, 109.9, 109.8, 109.6, 109.5, 103.54, 103.52,103.19, 103.17, 100.4, 100.1, 55.4, 55.2, 55.1, 55.0, 32.4, 32.2 (d, J = 9.3Hz), 10.9 (d, J = 3.0 Hz), 10.5; 31 P NMR (162 MHz, CDCl3) δ 31.55 (s), -1.97(s); HRMS (EI-TOF) m / z Calcd for C 48 H 50 O9P2Si [M] + 860.2772 found: 860.2774.

[0839] Example 193: I-193

[0840]

[0841] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.53–7.49 (m, 5H),7.34–7.29 (m, 1H), 7.23–7.16 (m, 1H), 6.99 (s, 4H), 3.76 (s, 12H), 3.21–2.82(m, 4H), 2.07 (d, J = 6.0 Hz, 24H), 1.64–1.20 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 158.23, 155.6, 153.9, 153.7, 150.2, 143.7, 141.0, 137.9, 134.1, 133.2, 131.5, 131.0, 130.0, 129.9, 128.9, 128.1, 128.0, 127.1, 125.9, 122.0,59.9, 31.6, 31.3, 16.0, 15.9, 14.7.; 31 P NMR (162 MHz, CDCl3) δ 29.07 (s), -5.13 (s); HRMS (EI-TOF) m / z Calcd for C 52 H 58 O5P2Si [M] + 852.3529 found: 852.3522.

[0842] Example 194: I-194

[0843]

[0844] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.53–7.49 (m, 5H),7.34–7.29 (m, 1H), 7.23–7.16 (m, 1H), 6.99 (s, 4H), 3.76 (s, 12H), 3.21–2.82(m, 4H), 2.07 (d, J = 6.0 Hz, 24H), 1.64–1.20 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 158.23, 155.6, 153.9, 153.7, 150.2, 143.7, 141.0, 137.9, 134.1, 133.2, 131.5, 131.0, 130.0, 129.9, 128.9, 128.1, 128.0, 127.1, 125.9, 122.0,59.9, 31.6, 31.3, 16.0, 15.9, 14.7.; 31 P NMR (162 MHz, CDCl3) δ 29.07 (s), -5.13 (s); HRMS (EI-TOF) m / z Calcd for C 52 H 58 O5P2Si [M] + 852.3529 found: 852.3530.

[0845] Example 195: I-195

[0846]

[0847] White solid 11H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.61 (s, 4H), 7.54–7.48 (m, 1H), 7.35–7.28 (m, 1H), 7.22–7.15 (m, 1H), 7.10 (s, 4H), 3.82 (s, 12H), 3.00–2.92 (m, 4H), 1.49–1.43 (m, 4H), 1.41 (d, J = 1.6 Hz, 72H); 13 13C NMR(100 MHz, CDCl3) δ 140.6, 139.3, 130.8, 129.5, 61.1, 35.00, 34.99, 31.6, 31.3, 30.5, 14.7; 31 31P NMR (162 MHz, CDCl3) δ 33.21 (s), -6.70 (s); HRMS (EI-TOF) m / z Calcd for C 76 H 106 O5P2Si [M] + : 1188.7115 found: 1188.7110.

[0848] Example 196: I-196

[0849]

[0850] White solid, 1 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.61 (s, 4H), 7.54–7.48 (m, 1H), 7.35–7.28 (m, 1H), 7.22–7.15 (m, 1H), 7.10 (s, 4H), 3.82 (s, 12H), 3.00–2.92 (m, 4H), 1.49–1.43 (m, 4H), 1.41 (d, J = 1.6 Hz, 72H); 13C NMR(100 MHz, CDCl3) δ 140.6, 139.3, 130.8, 129.5, 61.1, 35.00, 34.99, 31.6,31.3, 30.5, 14.7; 31 P NMR (162 MHz, CDCl3) δ 33.21 (s), -6.70 (s); HRMS (EI-TOF) m / z Calcd for C 76 H 106 O5P2Si [M] + : 1188.7115 found: 1188.7117.

[0851] Example 197: I-197

[0852]

[0853] White solid 1 H NMR (400 MHz, CDCl3) δ 7.96 (dd, J = 6.8, 1.2 Hz, 1H), 7.85 (td, J = 7.2, 1.6 Hz, 2H), 7.81 (dd, J = 7.6, 1.2 Hz, 1H), 7.72–7.66 (m,3H), 7.53–7.49 (m, 1H), 7.36–7.27 (m, 7H), 7.25–7.13 (m, 5H), 7.10–7.05 (m,2H), 3.08–2.77 (m, 4H), 2.48 (d, J = 0.8 Hz, 6H), 2.39 (d, J = 0.8 Hz, 6H),1.49–1.43 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 154.0, 153.8, 149.2, 144.2,143.7, 141.5, 139.1, 138.4, 136.9, 134.6, 132.8, 132.29, 132.27, 131.1,130.13, 130.11, 129.0, 128.9, 128.7, 128.1, 126.7, 126.4, 125.9, 122.0, 31.6,31.3, 21.2, 20.6, 14.7; 3131P NMR (162 MHz, CDCl3) δ 32.61 (s), -6.39 (s); HRMS(EI-TOF) m / z Calcd for C 44 H 42 OP2Si [M] + : 676.2480 found: 676.2476.

[0854] Example 198: I-198

[0855]

[0856] White solid, 1 1H NMR (400 MHz, CDCl3) δ 7.96 (dd, J = 6.8, 1.2 Hz, 1H),7.85 (td, J = 7.2, 1.6 Hz, 2H), 7.81 (dd, J = 7.6, 1.2 Hz, 1H), 7.72–7.66 (m,3H), 7.53–7.49 (m, 1H), 7.36–7.27 (m, 7H), 7.25–7.13 (m, 5H), 7.10–7.05 (m,2H), 3.08–2.77 (m, 4H), 2.48 (d, J = 0.8 Hz, 6H), 2.39 (d, J = 0.8 Hz, 6H),1.49–1.43 (m, 4H); 13 13C NMR (100 MHz, CDCl3) δ 154.0, 153.8, 149.2, 144.2,143.7, 141.5, 139.1, 138.4, 136.9, 134.6, 132.8, 132.29, 132.27, 131.1,130.13, 130.11, 129.0, 128.9, 128.7, 128.1, 126.7, 126.4, 125.9, 122.0, 31.6,31.3, 21.2, 20.6,​​​​​​​​​​Example 199: I-199

[0858]

[0859] White solid 1 H NMR (400 MHz, CDCl3) δ 8.00–7.93 (m, 5H), 7.81 (dd, J =7.6, 1.2 Hz, 1H), 7.76–7.66 (m, 5H), 7.60–7.54 (m, 4H), 7.52–7.48 (m, 1H),7.46–7.39 (m, 4H), 7.34–7.29 (m, 1H), 7.22–7.16 (m, 1H), 3.12–2.81 (m, 4H),1.77–1.33 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 154.0, 153.8, 151.0, 146.4,141.7, 138.3, 136.3, 135.2, 134.7, 134.2, 133.0, 131.8, 131.3, 130.2, 128.91,128.85, 128.8, 128.71, 128.70, 128.66, 128.1, 127.9, 126.3, 125.9, 125.8,122.0, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 34.47 (s), -6.81 (s); 19 FNMR (375 MHz, CDCl3) δ -63.10; HRMS (EI-TOF) m / z Calcd for C 44 H 30 F 12 OP2Si [M] + 892.1350 found: 892.1342.

[0860] Example 200: I-200

[0861]

[0862] White solid 1H NMR (400 MHz, CDCl3) δ 8.00–7.93 (m, 5H), 7.81 (dd, J =7.6, 1.2 Hz, 1H), 7.76–7.66 (m, 5H), 7.60–7.54 (m, 4H), 7.52–7.48 (m, 1H),7.46–7.39 (m, 4H), 7.34–7.29 (m, 1H), 7.22–7.16 (m, 1H), 3.12–2.81 (m, 4H),1.77–1.33 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 154.0, 153.8, 151.0, 146.4,141.7, 138.3, 136.3, 135.2, 134.7, 134.2, 133.0, 131.8, 131.3, 130.2, 128.91,128.85, 128.8, 128.71, 128.70, 128.66, 128.1, 127.9, 126.3, 125.9, 125.8,122.0, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 34.47 (s), -6.81 (s); 19 FNMR (375 MHz, CDCl3) δ -63.10; HRMS (EI-TOF) m / z Calcd for C 44 H 30 F 12 OP2Si [M] + 892.1350 found: 892.1352.

[0863] Example 201: I-201

[0864]

[0865] White solid 1H NMR (400 MHz, CDCl3) δ 7.96 (dd, J = 6.8, 1.2 Hz, 1H), 7.83–7.76 (m, 3H), 7.65 (t, J = 7.2 Hz, 1H), 7.60 (td, J = 7.2, 1.2 Hz, 2H),7.54–7.49 (m, 1H), 7.46 (dd, J = 7.2, 1.6 Hz, 2H), 7.38 (td, J = 7.2, 1.6 Hz,2H), 7.34–7.22 (m, 5H), 7.22–7.16 (m, 1H), 7.05 (dd, J = 7.6, 1.2 Hz, 2H),6.84 (dd, J = 7.2, 1.6 Hz, 2H), 3.78 (d, J = 1.2 Hz, 12H), 3.04–2.75 (m, 4H),1.78–1.09 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 165.3, 160.4, 154.3, 153.8,150.3, 146.1, 141.5, 138.4, 134.8, 133.9, 132.9, 130.3, 129.5, 128.9, 128.8,128.0, 126.6, 126.0, 123.1, 122.8, 122.3, 122.0, 113.4, 113.1, 56.1, 31.6,31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 26.61 (s), -2.17 (s); HRMS (EI-TOF) m / zCalcd for C 44 H 42 O5P2Si [M] + 740.2277 found: 740.2280.

[0866] Example 202: I-202

[0867]

[0868] White solid 1H NMR (400 MHz, CDCl3) δ 7.96 (dd, J = 6.8, 1.2 Hz, 1H), 7.83–7.76 (m, 3H), 7.65 (t, J = 7.2 Hz, 1H), 7.60 (td, J = 7.2, 1.2 Hz, 2H),7.54–7.49 (m, 1H), 7.46 (dd, J = 7.2, 1.6 Hz, 2H), 7.38 (td, J = 7.2, 1.6 Hz,2H), 7.34–7.22 (m, 5H), 7.22–7.16 (m, 1H), 7.05 (dd, J = 7.6, 1.2 Hz, 2H),6.84 (dd, J = 7.2, 1.6 Hz, 2H), 3.78 (d, J = 1.2 Hz, 12H), 3.04–2.75 (m, 4H),1.78–1.09 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 165.3, 160.4, 154.3, 153.8,150.3, 146.1, 141.5, 138.4, 134.8, 133.9, 132.9, 130.3, 129.5, 128.9, 128.8,128.0, 126.6, 126.0, 123.1, 122.8, 122.3, 122.0, 113.4, 113.1, 56.1, 31.6,31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 26.61 (s), -2.17 (s); HRMS (EI-TOF) m / zCalcd for C 44 H 42 O5P2Si [M] + 740.2277 found: 740.2283.

[0869] Example 203: I-203

[0870]

[0871] White solid 1H NMR (400 MHz, CDCl3) δ 8.21 (t, J = 2.0 Hz, 2H), 8.02 (dq,J = 7.2, 1.6 Hz, 5H), 7.93 (d, J = 8.0 Hz, 2H), 7.89–7.80 (m, 8H), 7.72 (dd,J = 7.6, 1.2 Hz, 1H), 7.71–7.65 (m, 3H), 7.55–7.48 (m, 9H), 7.37 (dd, J =8.0, 2.0 Hz, 2H), 7.34–7.29 (m, 1H), 7.23–7.16 (m, 1H), 3.35–2.74 (m, 4H), 1.58–1.07 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 153.9, 153.7, 150.5, 143.7,141.2, 137.8, 135.8, 135.7, 135.6, 134.9, 133.3, 132.9, 132.0, 131.1, 130.7,130.0, 129.3, 129.2, 129.1, 129.0, 128.9, 128.5, 128.3, 128.1, 128.0, 127.76,127.75, 127.6, 127.1, 125.9, 122.0, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3)δ 30.35 (s), -6.29 (s); HRMS (EI-TOF) m / z Calcd for C 56 H 42 OP2Si [M] + 820.2480 found: 820.2473.

[0872] Example 204: I-204

[0873]

[0874] White solid 1H NMR (400 MHz, CDCl3) δ 8.21 (t, J = 2.0 Hz, 2H), 8.02 (dq,J = 7.2, 1.6 Hz, 5H), 7.93 (d, J = 8.0 Hz, 2H), 7.89–7.80 (m, 8H), 7.72 (dd,J = 7.6, 1.2 Hz, 1H), 7.71–7.65 (m, 3H), 7.55–7.48 (m, 9H), 7.37 (dd, J =8.0, 2.0 Hz, 2H), 7.34–7.29 (m, 1H), 7.23–7.16 (m, 1H), 3.35–2.74 (m, 4H), 1.58–1.07 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 153.9, 153.7, 150.5, 143.7,141.2, 137.8, 135.8, 135.7, 135.6, 134.9, 133.3, 132.9, 132.0, 131.1, 130.7,130.0, 129.3, 129.2, 129.1, 129.0, 128.9, 128.5, 128.3, 128.1, 128.0, 127.76,127.75, 127.6, 127.1, 125.9, 122.0, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3)δ 30.35 (s), -6.29 (s); HRMS (EI-TOF) m / z Calcd for C 56 H 42 OP2Si [M] + 820.2480 found: 820.2483.

[0875] Example 205: I-205

[0876]

[0877] White solid 1H NMR (400 MHz, CDCl3) δ 7.46 (d, J = 8.0 Hz, 1H), 7.30 (td,J = 7.6, 3.2 Hz, 1H), 7.27–7.17 (m, 2H), 7.07–6.95 (m, 2H), 6.92 (d, J = 11.2Hz, 1H), 6.86 (d, J = 6.4 Hz, 1H), 6.82 (dd, J = 8.0, 2.4 Hz, 1H), 6.72 (d, J= 8.0 Hz, 1H), 6.63–6.50 (m, 5H), 6.47 (dd, J = 8.0, 2.4 Hz, 1H), 6.32 (d, J= 4.8 Hz, 1H), 6.27 (d, J = 8.8 Hz, 1H), 3.62–3.52 (m, 2H), 3.26–3.04 (m,2H), 1.59–1.48 (m, 1H), 1.17–1.04 (m, 1H), 1.04–0.83 (m, 2H); 13C NMR (100MHz, CDCl3) δ 157.7, 157.6, 155.4, 155.3, 150.33, 150.30, 149.99, 149.97,147.8, 147.74, 147.65, 147.60, 147.57, 6, 130.4, 130.3, 130.1, 129.8, 129.4, 128.7, 128.6, 128.5, 128.2, 128.0, 127.33, 127.28, 127.22, 127.17, 127.1, 127.0, 126.9, 126.6, 126.3, 125.2, 113.4, 113.2, 112.5, 112.3, 111.5, 111.41, 111.37, 111.3, 108.5, 108.44, 108.36, 108.3, 108.14, 108.08, 108.0, 107.9, 101.4, 101.2, 100.8, 100.7,32.5, 32.3 (d, J = 9.8 Hz), 11.0 (d, J = 3.4 Hz), 10.5; 31 P NMR (162 MHz, CDCl3) δ 30.45 (s), -4.77 (s); HRMS (EI-TOF) m / z Calcd for C 44 H 34 O9P2Si [M] + 796.1520 found: 796.1527.

[0878] Example 206: I-206

[0879]

[0880] White solid 1H NMR (400 MHz, CDCl3) δ 7.46 (d, J = 8.0 Hz, 1H), 7.30 (td,J = 7.6, 3.2 Hz, 1H), 7.27–7.17 (m, 2H), 7.07–6.95 (m, 2H), 6.92 (d, J = 11.2Hz, 1H), 6.86 (d, J = 6.4 Hz, 1H), 6.82 (dd, J = 8.0, 2.4 Hz, 1H), 6.72 (d, J= 8.0 Hz, 1H), 6.63–6.50 (m, 5H), 6.47 (dd, J = 8.0, 2.4 Hz, 1H), 6.32 (d, J= 4.8 Hz, 1H), 6.27 (d, J = 8.8 Hz, 1H), 3.62–3.52 (m, 2H), 3.26–3.04 (m,2H), 1.59–1.48 (m, 1H), 1.17–1.04 (m, 1H), 1.04–0.83 (m, 2H); 13C NMR (100MHz, CDCl3) δ 157.7, 157.6, 155.4, 155.3, 150.33, 150.30, 149.99, 149.97,147.8, 147.74, 147.65, 147.60, 147.57, 6, 130.4, 130.3, 130.1, 129.8, 129.4, 128.7, 128.6, 128.5, 128.2, 128.0, 127.33, 127.28, 127.22, 127.17, 127.1, 127.0, 126.9, 126.6, 126.3, 125.2, 113.4, 113.2, 112.5, 112.3, 111.5, 111.41, 111.37, 111.3, 108.5, 108.44, 108.36, 108.3, 108.14, 108.08, 108.0, 107.9, 101.4, 101.2, 100.8, 100.7,32.5, 32.3 (d, J = 9.8 Hz), 11.0 (d, J = 3.4 Hz), 10.5; 31 P NMR (162 MHz, CDCl3) δ 30.45 (s), -4.77 (s); HRMS (EI-TOF) m / z Calcd for C 44 H 34 O9P2Si [M] + 796.1520 found: 796.1518.

[0881] Example 207: I-207

[0882]

[0883] White solid 1H NMR (400 MHz, CDCl3) δ 8.43 (dd, J = 6.8, 1.2 Hz, 1H), 8.02 (dd, J = 7.6, 1.2 Hz, 1H), 7.78 (dt, J = 7.6, 1.6 Hz, 2H), 7.68–7.60 (m,3H), 7.57–7.46 (m, 7H), 7.43 (dddd, J = 8.8, 7.6, 3.6, 1.2 Hz, 4H), 7.38–7.27(m, 7H), 7.22–7.16 (m, 1H), 3.21–2.77 (m, 4H), 1.65–1.17 (m, 4H); 13 C NMR (100MHz, CDCl3) δ 156.1, 154.3, 154.1, 153.7, 150.8, 146.7, 145.1, 140.7, 140.0,136.8, 129.7, 129.0, 128.94, 128.93, 128.1, 127.0, 126.9, 126.8, 126.5,126.0, 125.0, 124.9, 123.5, 122.5, 122.1, 112.9, 112.6, 112.0, 108.9, 31.6,31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 6.30 (s), -1.77 (s); HRMS (EI-TOF) m / zCalcd for C 48 H 34 O5P2Si [M] + 780.1651 found: 780.1650.

[0884] Example 208: I-208

[0885]

[0886] White solid 1H NMR (400 MHz, CDCl3) δ 8.43 (dd, J = 6.8, 1.2 Hz, 1H), 8.02 (dd, J = 7.6, 1.2 Hz, 1H), 7.78 (dt, J = 7.6, 1.6 Hz, 2H), 7.68–7.60 (m,3H), 7.57–7.46 (m, 7H), 7.43 (dddd, J = 8.8, 7.6, 3.6, 1.2 Hz, 4H), 7.38–7.27(m, 7H), 7.22–7.16 (m, 1H), 3.21–2.77 (m, 4H), 1.65–1.17 (m, 4H); 13 C NMR (100MHz, CDCl3) δ 156.1, 154.3, 154.1, 153.7, 150.8, 146.7, 145.1, 140.7, 140.0,136.8, 129.7, 129.0, 128.94, 128.93, 128.1, 127.0, 126.9, 126.8, 126.5,126.0, 125.0, 124.9, 123.5, 122.5, 122.1, 112.9, 112.6, 112.0, 108.9, 31.6,31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 6.30 (s), -1.77 (s); HRMS (EI-TOF) m / zCalcd for C 48 H 34 O5P2Si [M] + 780.1651 found: 780.1653.

[0887] Example 209: I-209

[0888]

[0889] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H),7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.54–7.48 (m, 1H),7.43 (dd, J = 9.2, 2.0 Hz, 2H), 7.34–7.29 (m, 1H), 7.27 (d, J = 2.0 Hz, 2H), 7.23–7.16 (m, 1H), 6.95–6.87 (m, 6H), 6.84 (d, J = 9.6 Hz, 2H), 4.29 (d, J =2.8 Hz, 16H), 3.23–2.80 (m, 4H), 1.52–1.26 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ154.0, 153.8, 150.2, 146.8, 146.4, 145.9, 143.8, 143.6, 141.3, 138.0, 131.8,130.2, 130.0, 128.9, 128.3, 128.1, 128.0, 126.8, 125.9, 122.0, 118.8, 115.8,115.4, 115.3, 64.4, 64.2, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 29.61(s), -5.02 (s); HRMS (EI-TOF) m / z Calcd for C 48 H 42 O9P2Si [M] + 852.2073 found: 852.2069.

[0890] Example 210: I-210

[0891]

[0892] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H),7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.69 (t, J = 7.2 Hz, 1H), 7.54–7.48 (m, 1H),7.43 (dd, J = 9.2, 2.0 Hz, 2H), 7.34–7.29 (m, 1H), 7.27 (d, J = 2.0 Hz, 2H), 7.23–7.16 (m, 1H), 6.95–6.87 (m, 6H), 6.84 (d, J = 9.6 Hz, 2H), 4.29 (d, J =2.8 Hz, 16H), 3.23–2.80 (m, 4H), 1.52–1.26 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ154.0, 153.8, 150.2, 146.8, 146.4, 145.9, 143.8, 143.6, 141.3, 138.0, 131.8,130.2, 130.0, 128.9, 128.3, 128.1, 128.0, 126.8, 125.9, 122.0, 118.8, 115.8,115.4, 115.3, 64.4, 64.2, 31.6, 31.3, 14.7; 31 P NMR (162 MHz, CDCl3) δ 29.61(s), -5.02 (s); HRMS (EI-TOF) m / z Calcd for C 48 H 42 O9P2Si [M] + 852.2073 found: 852.2070.

[0893] Example 211: Synthesis of compound I-211

[0894]

[0895] In a nitrogen atmosphere, A-1 (29.3 g, 100 mmol), triphenylphosphine (31.5 g, 120 mmol), tetrabutylammonium iodide (44.4 g, 120 mmol), and ultradry dibromoethane (400 mL) were placed in a sealed tube and heated to 60°C. oThe reaction was carried out at C for 5 hours. After cooling to room temperature and removing the solvent under reduced pressure, the mixture was purified by column chromatography to give a white solid A-2 (30.3 g, yield: 85%).

[0896] 0 o C. Vinyl magnesium bromide (150 mL, 1.0 M in THF, 150 mmol) was slowly added dropwise to an ultra-dry toluene (120 mL) solution containing A-2 (30.3 g, 85 mmol), cuprous iodide (1.6 g, 8.5 mmol), and 2,2'-bipyridine (1.3 g, 8.5 mmol). After the addition was complete, the reaction was allowed to return to room temperature and stirred continuously. After the reaction was confirmed to be complete by TLC, the reaction was quenched with saturated ammonium chloride aqueous solvent. The aqueous phase was extracted three times with diethyl ether. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, evaporated to dryness, and purified by column chromatography to obtain a colorless liquid A-3 (21.1 g, yield: 82%).

[0897] In a nitrogen atmosphere, -78 o At temperature C, 27.2 mL of 2.5 M hexane (68 mmol) was slowly added dropwise to a 100 mL solution of tetrahydrofuran (20.6 g, 68 mmol) of A-3. The solution was kept at -78°C after the addition was complete. o The reaction at C was carried out for 1 hour. Subsequently, tetrachlorosilane (5.78 g, 34 mmol) was added dropwise to the system, and the temperature was maintained at -78°C. o After reacting at C for 30 minutes, the mixture was brought back to room temperature and stirred for 8 hours. The system was then placed in an ice-water bath, and vinyl magnesium bromide (150 mL, 1.0 M in THF, 150 mmol) was added dropwise. After the addition was complete, the mixture was kept at 30°C. o The reaction was carried out for 10 hours. The reaction system was quenched with water, followed by the addition of dichloromethane. The organic phase was dried with anhydrous sodium sulfate, filtered, and evaporated to dryness before being purified by column chromatography to obtain a colorless liquid A-4 (10.8 g, yield: 61%).

[0898] Under a nitrogen atmosphere, A-4 (10.6 g, 20 mmol), Grubbs first-generation catalyst (82.4 mg, 0.1 mmol), and dichloromethane (20 mL) were placed in a 100 mL dry Schlenk flask, stirred at room temperature for 30 minutes, and then heated to 55°C. o C reaction. After the reaction was confirmed to be complete by TLC, the reaction was cooled to room temperature and purified by column chromatography to obtain colorless liquid A-5 (9.4 g, yield: 99%).

[0899] A-5 (9.4 g, 19.8 mmol) was dissolved in ethyl acetate (50 mL), and then Pd(OH)2 / C (1 g) was added. After purging the reaction flask with hydrogen three times, the solution was added at 45 °C. o The reaction proceeded at C until the starting material disappeared. The Pd(OH)2 / C was removed by filtration through a short silica gel column. The filtrate was then evaporated to dryness and purified by column chromatography to obtain a colorless liquid A-6 (5.4 g, yield: 92%).

[0900] A solution of tetrabutylammonium bromide (3.24 g, 10 mmol) in chloroform (52 ​​mL) was added to a solution of A-6 (5.4 g, 18.5 mmol) and sodium hydroxide (3.3 g, 81.4 mmol) in water (52 mL), followed by the addition of menthyl (-)-chloroformate (12.3 g, 56.1 mmol). After the reaction was complete, the aqueous phase was extracted three times with dichloromethane. The organic phases were combined and dried over anhydrous sodium sulfate, allowed to stand, filtered off the drying agent, evaporated to dryness, and purified by column chromatography to give a pale yellow solid, a mixture of A-7 and A-7' (10.3 g, yield: 85%). A mixture of A-7 and A-7' was recrystallized (petroleum ether-dichloromethane system) to give a white solid A-7' (4.7 g, yield: 46%). The remaining mother liquor was dried by rotary evaporation and then recrystallized (petroleum ether-acetone system) to give a pale yellow solid A-7 (4.5 g, yield: 44%).

[0901] Potassium hydroxide (2.7 g, 68 mmol) was added to a solution of A-7 (4.5 g, 6.85 mmol) in methanol (90 mL) and water (12 mL), and the system was refluxed until the reaction was complete. After returning to room temperature, some methanol was evaporated, and the mixture was extracted twice with n-hexane. The aqueous phase was acidified with 6 M hydrochloric acid to pH 6, resulting in a white precipitate. This precipitate was then extracted with diethyl ether, and the organic phase was separated. The precipitate was dried over anhydrous sodium sulfate, allowed to stand, filtered to remove the drying agent, and evaporated to dryness to give a colorless liquid II-2 (1.9 g, yield: 95%). The same method was used to obtain a white solid II-3 (2.0 g, yield: 96%) from A-7' (4.7 g, 7.15 mmol).

[0902]

[0903] Under nitrogen protection, chiral bis(2-2) spirobis(dihydrobenzothiophene) bisphenol II-2 (7.61 g, 25.7 mmol), dichloromethane (128.5 mL), and pyridine (8.93 g, 113.1 mmol) were added to a 500 mL dry three-necked flask. The flask was then placed in an ice bath, and trifluoromethanesulfonic anhydride (16.7 g, 59.1 mmol) was slowly added dropwise. After the addition was complete, the mixture was stirred for 10 minutes, then the flask was removed from the ice bath, and the reaction system was allowed to return to room temperature (25 °C). o C) Stirring. The reaction was monitored by TLC until complete. The solvent was removed using a rotary evaporator. Ethyl acetate was added, and the mixture was washed successively with saturated sodium bicarbonate aqueous solution and saturated brine. The organic phase was dried over anhydrous sodium sulfate, filtered, and purified by column chromatography after solvent removal using a rotary evaporator to obtain III-2 (10.1 g, yield: 70%).

[0904]

[0905] White solid 1 H NMR (400 MHz, CDCl3) δ 7.37 (dd, J = 7.6, 1.2 Hz, 2H), 7.29–7.23 (m, 2H), 7.20 (t, J = 7.6 Hz, 2H), 2.66–2.59 (m, 2H), 2.55–2.48 (m, 2H), 1.88–1.78 (m, 4H), 1.39–1.31 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 158.4,151.6, 132.7, 130.9, 119.2, 117.3, 116.4, 38.0, 21.6, 11.8; 19 F NMR (375 MHz, CDCl3) δ -74.12; HRMS (ESI-TOF) m / z Calcd for C 20 H 18 F6O6S2Si [M] + : 560.0218, found: 560.0215.

[0906]

[0907] Under nitrogen protection, chiral spirobis(dihydrobenzothiopyrrolidone) trifluoromethanesulfonate III-2 (5.60 g, 10 mmol), diphenylphosphine oxide (2.5 g, 13 mmol), palladium acetate (112.5 mg, 0.5 mmol), 1,4-bis(diphenylphosphine)butane (256 mg, 0.6 mmol), degassed dimethyl sulfoxide (100 mL), and N,N-diisopropylethylamine (5.2 g, 40 mmol) were added to a 250 mL dry sealed tube. The tube was sealed at 110 °C. o After heating in an oil bath for 11 hours, the mixture was cooled to room temperature. The reaction system was then extracted with ethyl acetate, and the solvent was removed by rotary evaporation followed by column chromatography purification to obtain IV-2 (4.5 g, yield: 73%).

[0908]

[0909] White solid 1 H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.68–7.61 (m, 5H), 7.57–7.49 (m, 3H), 7.49–7.42 (m, 4H), 7.37 (dd, J = 7.6, 1.2 Hz, 1H), 7.29–7.23 (m, 1H), 7.20 (t, J = 7.6 Hz, 1H), 2.66–2.59 (m, 2H), 2.58–2.48 (m, 2H), 1.88–1.78 (m, 4H), 1.30–1.23 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 13 C NMR (125 MHz, Common NMR Solvents) δ 158.4, 152.3, 151.0, 143.6,139.6, 133.3, 132.4, 132.3, 131.9, 130.9, 130.2, 129.5, 128.9, 128.3, 119.2,117.3, 116.4, 38.0, 37.4, 21.6, 11.8; 31 P NMR (162 MHz, CDCl3) δ 33.71 (s); 19 FNMR (375 MHz, CDCl3) δ -74.25; HRMS (ESI-TOF) m / z Calcd for C 31 H28 F3O4PSSi [M] + :612.1167, found: 612.1165.

[0910]

[0911] Under nitrogen protection, chiral spirobis(dihydrobenzothiophene)diphenylphosphine oxide IV-2 (1.2 g, 2 mmol), toluene (10.0 mL), and N,N-diisopropylethylamine (21.2 g, 164 mmol) were added to a 250 mL dry three-necked flask. The flask was then placed in an ice bath, and trichlorosilane (8.46 g, 62.4 mmol) was added. After refluxing the reaction system for 10 hours, it was cooled to room temperature and placed in an ice bath. The mixture was diluted with diethyl ether, and the reaction was quenched dropwise with saturated sodium bicarbonate solution. The mixture was filtered through diatomaceous earth, and the filtrate was evaporated by rotary evaporation to remove most of the solvent. The filtrate was then extracted with ethyl acetate, and the organic phases were combined, dried over anhydrous sodium sulfate, and purified by column chromatography after further solvent removal using a rotary evaporator to obtain V-2 (0.5 g, yield: 90%).

[0912]

[0913] White solid 1 H NMR (400 MHz, CDCl3) δ 7.72 (dd, J = 7.6, 1.2 Hz, 1H),7.40–7.34 (m, 3H), 7.34–7.27 (m, 5H), 7.27–7.23 (m, 1H), 7.21 (td, J = 7.6,3.6 Hz, 2H), 7.15–7.09 (m, 4H), 2.68–2.59 (m, 2H), 2.59–2.48 (m, 2H), 1.88–1.78 (m, 4H), 1.21–1.09 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 158.4, 154.1,153.3, 151.0, 145.3, 136.9, 134.0, 131.6, 130.94, 130.92, 129.3, 128.4,128.1, 125.7, 119.2, 117.3, 116.4, 38.0, 37.7, 21.6, 12.0; 31 P NMR (162 MHz, CDCl3) δ -6.51 (s); 19F NMR (375 MHz, CDCl3) δ -74.30; HRMS (ESI-TOF) m / zCalcd for C 31 H 28 F3O3PSSi [M] + : 596.1218, found: 596.1213.

[0914]

[0915] Under nitrogen protection, chiral spirobis(dihydrobenzothiophene) monophosphine compound V-1 (5.68 g, 10 mmol), diphenylphosphine oxide (10.1 g, 50 mmol), palladium acetate (112.5 mg, 0.5 mmol), 1,4-bis(diphenylphosphine)butane (256 mg, 0.6 mmol), degassed dimethyl sulfoxide (100 mL), and N,N-diisopropylethylamine (5.2 g, 40 mmol) were added to a 250 mL dry sealed tube. The tube was sealed at 110 °C. o After heating in an oil bath for 10 hours, the mixture was cooled to room temperature. The reaction system was then extracted with ethyl acetate, and the solvent was removed by rotary evaporation followed by column chromatography purification to obtain IV-1 (5.0 g, yield: 95%).

[0916]

[0917] White solid 1 H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.68–7.61 (m, 5H), 7.57–7.49 (m, 3H), 7.49–7.43 (m, 4H), 7.39–7.35 (m, 2H), 7.35–7.26 (m, 5H), 7.24–7.18 (m, 1H), 7.15–7.09 (m, 4H), 2.66–2.59 (m, 2H), 2.59–2.48 (m, 2H), 1.88–1.78 (m, 4H), 1.11–1.03 (m, 4H); 13C NMR (100 MHz, CDCl3) δ 154.2, 153.4, 151.6, 144.6, 143.5,138.5, 137.0, 134.0, 133.3, 132.3, 131.9, 130.9, 130.2, 129.5, 129.3, 128.9,128.4, 128.3, 128.1, 125.7, 37.7, 37.4, 21.6, 12.0; 31 P NMR (162 MHz, CDCl3) δ33.75 (s), -6.61 (s); HRMS (EI-TOF) m / z Calcd for C 42 H 38 OP2Si [M] + 648.2167 found: 648.2160.

[0918] Following the same procedures and feed methods as in Example 211, and using the corresponding raw materials, compounds I-212 to I-228 were prepared.

[0919] Example 212: I-212

[0920]

[0921] White solid 1 H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.68–7.61 (m, 5H), 7.57–7.49 (m, 3H), 7.49–7.43 (m, 4H), 7.39–7.35 (m, 2H), 7.35–7.26 (m, 5H), 7.24–7.18 (m, 1H), 7.15–7.09 (m, 4H), 2.66–2.59 (m, 2H), 2.59–2.48 (m, 2H), 1.88–1.78 (m, 4H), 1.11–1.03 (m, 4H); 13C NMR (100 MHz, CDCl3) δ 154.2, 153.4, 151.6, 144.6, 143.5,138.5, 137.0, 134.0, 133.3, 132.3, 131.9, 130.9, 130.2, 129.5, 129.3, 128.9,128.4, 128.3, 128.1, 125.7, 37.7, 37.4, 21.6, 12.0; 31 P NMR (162 MHz, CDCl3) δ33.75 (s), -6.61 (s); HRMS (EI-TOF) m / z Calcd for C 42 H 38 OP2Si [M] + 648.2167 found: 648.2165.

[0922] Example 213: I-213

[0923]

[0924] White solid 1 H NMR (400 MHz, CDCl3) δ 8.24 (dd, J = 7.6, 1.2 Hz, 1H), 7.88 (dd, J = 8.4, 1.2 Hz, 1H), 7.69 (t, J = 7.6 Hz, 1H), 7.50 (dd, J = 7.2, 1.2 Hz, 1H), 7.29 (dd, J = 7.2, 1.2 Hz, 1H), 7.13 (dd, J = 8.4, 7.2 Hz, 1H), 2.72–2.59 (m, 4H), 2.58–2.52 (m, 2H), 2.52–2.44 (m, 2H), 1.96–1.76 (m, 12H),1.75–1.65 (m, 4H), 1.65–1.30 (m, 28H), 1.11–1.03 (m, 4H); 13C NMR (100 MHz, CDCl3) δ 159.2, 155.0, 154.6, 144.3, 141.4, 140.3, 130.9, 129.5, 129.2,127.9, 126.3, 125.7, 37.7, 37.4, 34.2, 31.1, 29.8, 29.5, 27.0, 26.8, 26.5,26.0, 21.6, 12.0; 31 P NMR (162 MHz, CDCl3) δ 49.24 (s), -7.22 (s); HRMS (EI-TOF) m / z Calcd for C 42 H 62 OP2Si [M] + Found: 672.4045; Found: 672.4037.

[0925] Example 214: I-214

[0926]

[0927] White solid 1 H NMR (400 MHz, CDCl3) δ 8.24 (dd, J = 7.6, 1.2 Hz, 1H), 7.88 (dd, J = 8.4, 1.2 Hz, 1H), 7.69 (t, J = 7.6 Hz, 1H), 7.50 (dd, J = 7.2, 1.2 Hz, 1H), 7.29 (dd, J = 7.2, 1.2 Hz, 1H), 7.13 (dd, J = 8.4, 7.2 Hz, 1H), 2.72–2.59 (m, 4H), 2.58–2.52 (m, 2H), 2.52–2.44 (m, 2H), 1.96–1.76 (m, 12H),1.75–1.65 (m, 4H), 1.65–1.30 (m, 28H), 1.11–1.03 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 159.2, 155.0, 154.6, 144.3, 141.4, 140.3, 130.9, 129.5, 129.2,127.9, 126.3, 125.7, 37.7, 37.4, 34.2, 31.1, 29.8, 29.5, 27.0, 26.8, 26.5,26.0, 21.6, 12.0;31 P NMR (162 MHz, CDCl3) δ 49.24 (s), -7.22 (s); HRMS (EI-TOF) m / z Calcd for C 42 H 62 OP2Si [M] + Found: 672.4045; Found: 672.4046.

[0928] Example 215: I-215

[0929]

[0930] White solid 1 H NMR (400 MHz, CDCl3) δ 7.81 (dd, J = 5.2, 1.2 Hz, 1H), 7.77 (dd, J = 7.2, 5.2 Hz, 1H), 7.54–7.47 (m, 2H), 7.31–7.27 (m, 1H), 7.26–7.22 (m, 1H), 2.66–2.60 (m, 2H), 2.59–2.50 (m, 2H), 1.88–1.78 (m, 4H), 1.27(s, 18H), 1.15 (s, 18H), 1.11–1.03 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 155.8,155.6, 151.8, 148.0, 136.8, 134.2, 131.6, 130.7, 130.5, 130.2, 129.5, 125.7,42.0, 37.7, 37.4, 29.9, 29.4, 26.5, 21.6, 12.0; 31 P NMR (162 MHz, CDCl3) δ48.73 (s), -12.77 (s); HRMS (EI-TOF) m / z Calcd for C 34 H 54 OP2Si [M] + 568.3419 found: 568.3413.

[0931] Example 216: I-216

[0932]

[0933] White solid 1H NMR (400 MHz, CDCl3) δ 7.81 (dd, J = 5.2, 1.2 Hz, 1H), 7.77 (dd, J = 7.2, 5.2 Hz, 1H), 7.54–7.47 (m, 2H), 7.31–7.27 (m, 1H), 7.26–7.22 (m, 1H), 2.66–2.60 (m, 2H), 2.59–2.50 (m, 2H), 1.88–1.78 (m, 4H), 1.27(s, 18H), 1.15 (s, 18H), 1.11–1.03 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 155.8,155.6, 151.8, 148.0, 136.8, 134.2, 131.6, 130.7, 130.5, 130.2, 129.5, 125.7,42.0, 37.7, 37.4, 29.9, 29.4, 26.5, 21.6, 12.0; 31 P NMR (162 MHz, CDCl3) δ48.73 (s), -12.77 (s); HRMS (EI-TOF) m / z Calcd for C 34 H 54 OP2Si [M] + 568.3419 found: 568.3418.

[0934] Example 217: I-217

[0935]

[0936] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.65 (t, J = 7.2 Hz, 1H), 7.63–7.57 (m, 4H),7.54–7.49 (m, 1H), 7.32–7.27 (m, 1H), 7.26–7.15 (m, 9H), 7.11–7.05 (m, 4H),2.65–2.59 (m, 2H), 2.58–2.53 (m, 2H), 2.43–2.40 (m, 12H), 1.88–1.78 (m, 4H), 1.11–1.03 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 154.3, 153.4, 151.6, 144.6,143.4, 141.5, 138.7, 138.5, 135.2, 135.0, 132.9, 130.9, 130.2, 129.9, 129.8,129.5, 129.3, 129.0, 128.9, 125.7, 37.7, 37.4, 21.6, 21.27, 21.26, 12.0; 31 PNMR (162 MHz, CDCl3) δ 33.50 (s), -10.45 (s); HRMS (EI-TOF) m / z Calcd forC 46 H 46 OP2Si [M] + 704.2793 found: 704.2798.

[0937] Example 218: I-218

[0938]

[0939] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.65 (t, J = 7.2 Hz, 1H), 7.63–7.57 (m, 4H),7.54–7.49 (m, 1H), 7.32–7.27 (m, 1H), 7.26–7.15 (m, 9H), 7.11–7.05 (m, 4H),2.65–2.59 (m, 2H), 2.58–2.53 (m, 2H), 2.43–2.40 (m, 12H), 1.88–1.78 (m, 4H), 1.11–1.03 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 154.3, 153.4, 151.6, 144.6,143.4, 141.5, 138.7, 138.5, 135.2, 135.0, 132.9, 130.9, 130.2, 129.9, 129.8,129.5, 129.3, 129.0, 128.9, 125.7, 37.7, 37.4, 21.6, 21.27, 21.26, 12.0; 31 PNMR (162 MHz, CDCl3) δ 33.50 (s), -10.45 (s); HRMS (EI-TOF) m / z Calcd forC 46 H 46 OP2Si [M] + 704.2793 found: 704.2790.

[0940] Example 219: I-219

[0941]

[0942] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.68–7.62 (m, 5H), 7.54–7.48 (m, 1H), 7.38–7.32 (m, 4H), 7.30–7.27 (m, 1H), 7.24–7.16 (m, 1H), 6.99–6.85 (m, 8H), 3.83(s, 12H), 2.66–2.59 (m, 2H), 2.58–2.51 (m, 2H), 1.88–1.78 (m, 4H), 1.11–1.03 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 162.5, 160.4, 154.2, 153.2, 151.6, 144.7,143.6, 138.4, 136.5, 134.3, 131.8, 130.9, 130.2, 129.5, 129.3, 128.9, 125.8,125.7, 115.2, 114.4, 55.3, 37.7, 37.4, 21.6, 12.0; 31 P NMR (162 MHz, CDCl3) δ33.09 (s), -10.38 (s); HRMS (EI-TOF) m / z Calcd for C 46 H 46 O5P2Si [M] + 768.2590 found: 768.2596.

[0943] Example 220: I-220

[0944]

[0945] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.68–7.62 (m, 5H), 7.54–7.48 (m, 1H), 7.38–7.32 (m, 4H), 7.30–7.27 (m, 1H), 7.24–7.16 (m, 1H), 6.99–6.85 (m, 8H), 3.83(s, 12H), 2.66–2.59 (m, 2H), 2.58–2.51 (m, 2H), 1.88–1.78 (m, 4H), 1.11–1.03 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 162.5, 160.4, 154.2, 153.2, 151.6, 144.7,143.6, 138.4, 136.5, 134.3, 131.8, 130.9, 130.2, 129.5, 129.3, 128.9, 125.8,125.7, 115.2, 114.4, 55.3, 37.7, 37.4, 21.6, 12.0; 31 P NMR (162 MHz, CDCl3) δ33.09 (s), -10.38 (s); HRMS (EI-TOF) m / z Calcd for C 46 H 46 O5P2Si [M] + 768.2590 found: 768.2592.

[0946] Example 221: I-221

[0947]

[0948] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.87–7.80 (m, 4H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.68–7.59 (m, 9H), 7.54–7.48 (m, 5H), 7.32–7.27 (m, 1H), 7.24–7.18 (m, 1H), 2.66–2.59 (m, 2H), 2.59–2.51 (m, 2H), 1.88–1.78 (m, 4H), 1.11–1.03 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ154.2, 153.2, 151.6, 144.7, 143.4, 138.5, 137.0, 135.5, 133.6, 133.5, 131.8,131.5, 130.9, 130.2, 129.5, 129.3, 128.9, 127.1, 126.1, 125.7, 124.0, 37.7,37.4, 21.6, 12.0; 31 P NMR (162 MHz, CDCl3) δ 32.14 (s), -8.16 (s); 19 F NMR (375MHz, CDCl3) δ -63.34; HRMS (EI-TOF) m / z Calcd for C 46 H 34 F 12 OP2Si [M] + 920.1663 found: 920.1665.

[0949] Example 222: I-222

[0950]

[0951] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.87–7.80 (m, 4H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.68–7.59 (m, 9H), 7.54–7.48 (m, 5H), 7.32–7.27 (m, 1H), 7.24–7.18 (m, 1H), 2.66–2.59 (m, 2H), 2.59–2.51 (m, 2H), 1.88–1.78 (m, 4H), 1.11–1.03 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ154.2, 153.2, 151.6, 144.7, 143.4, 138.5, 137.0, 135.5, 133.6, 133.5, 131.8,131.5, 130.9, 130.2, 129.5, 129.3, 128.9, 127.1, 126.1, 125.7, 124.0, 37.7,37.4, 21.6, 12.0; 31 P NMR (162 MHz, CDCl3) δ 32.14 (s), -8.16 (s); 19 F NMR (375MHz, CDCl3) δ -63.34; HRMS (EI-TOF) m / z Calcd for C 46 H 34 F 12 OP2Si [M] + 920.1663 found: 920.1660.

[0952] Example 223: I-223

[0953]

[0954] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.68–7.62 (m, 1H), 7.55–7.50 (m, 1H), 7.48(d, J = 2.0 Hz, 4H), 7.32–7.27 (m, 1H), 7.24–7.18 (m, 1H), 7.00 (dt, J = 2.4,1.2 Hz, 2H), 6.95–6.88 (m, 6H), 2.66–2.59 (m, 2H), 2.59–2.51 (m, 2H), 2.17(d, J = 18.4 Hz, 24H), 1.88–1.78 (m, 4H), 1.11–1.03 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 154.2, 151.7, 151.6, 144.7, 142.5, 140.4, 139.1, 138.4, 137.0,132.5, 132.3, 131.0, 130.92, 130.90, 130.2, 129.5, 129.31, 129.28, 128.9,125.7, 37.7, 37.4, 21.6, 21.1, 12.0; 31 P NMR (162 MHz, CDCl3) δ 32.98 (s), -9.54 (s); HRMS (EI-TOF) m / z Calcd for C 50 H 54 OP2Si [M] + 760.3419 found: 760.3413.

[0955] Example 224: I-224

[0956]

[0957] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.68–7.62 (m, 1H), 7.55–7.50 (m, 1H), 7.48(d, J = 2.0 Hz, 4H), 7.32–7.27 (m, 1H), 7.24–7.18 (m, 1H), 7.00 (dt, J = 2.4,1.2 Hz, 2H), 6.95–6.88 (m, 6H), 2.66–2.59 (m, 2H), 2.59–2.51 (m, 2H), 2.17(d, J = 18.4 Hz, 24H), 1.88–1.78 (m, 4H), 1.11–1.03 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 154.2, 151.7, 151.6, 144.7, 142.5, 140.4, 139.1, 138.4, 137.0,132.5, 132.3, 131.0, 130.92, 130.90, 130.2, 129.5, 129.31, 129.28, 128.9,125.7, 37.7, 37.4, 21.6, 21.1, 12.0; 31 P NMR (162 MHz, CDCl3) δ 32.98 (s), -9.54 (s); HRMS (EI-TOF) m / z Calcd for C 50 H 54 OP2Si [M] + 760.3419 found: 760.3420.

[0958] Example 225: I-225

[0959]

[0960] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.68–7.61 (m, 5H), 7.54–7.49 (m, 1H), 7.33 (dt, J = 8.0, 2.0 Hz, 4H), 7.32–7.27 (m, 1H), 7.24–7.18 (m, 1H), 7.16 (d, J =2.4 Hz, 4H), 2.66–2.59 (m, 2H), 2.59–2.51 (m, 2H), 1.88–1.78 (m, 4H), 1.36(s, 72H), 1.11–1.03 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 153.7, 153.2, 128.9,127.4, 125.3, 124.0, 37.7, 37.4, 34.97, 34.95, 31.3, 21.6, 12.0; 31 P NMR (162MHz, CDCl3) δ 33.28 (s), -10.63 (s); HRMS (EI-TOF) m / z Calcd for C 74 H 102 OP2Si[M] + : 1096.7175 found: 1096.7173.

[0961] Example 226: I-226

[0962]

[0963] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.68–7.61 (m, 5H), 7.54–7.49 (m, 1H), 7.33 (dt, J = 8.0, 2.0 Hz, 4H), 7.32–7.27 (m, 1H), 7.24–7.18 (m, 1H), 7.16 (d, J =2.4 Hz, 4H), 2.66–2.59 (m, 2H), 2.59–2.51 (m, 2H), 1.88–1.78 (m, 4H), 1.36(s, 72H), 1.11–1.03 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 153.7, 153.2, 128.9,127.4, 125.3, 124.0, 37.7, 37.4, 34.97, 34.95, 31.3, 21.6, 12.0; 31 P NMR (162MHz, CDCl3) δ 33.28 (s), -10.63 (s); HRMS (EI-TOF) m / z Calcd for C 74 H 102 OP2Si[M] + 1096.7175 found: 1096.7177.

[0964] Example 227: I-227

[0965]

[0966] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.65 (t, J = 7.2 Hz, 1H), 7.61 (s, 4H), 7.55–7.48 (m, 1H), 7.31–7.27 (m, 1H), 7.24–7.17 (m, 1H), 7.10 (s, 4H), 3.82 (s,12H), 2.65–2.59 (m, 2H), 2.59–2.51 (m, 2H), 1.88–1.78 (m, 4H), 1.41 (d, J =1.6 Hz, 72H), 1.11–1.03 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 140.6, 139.3, 130.8, 129.5, 61.1, 37.7, 37.4, 35.00, 34.99, 30.5, 21.6, 12.0; 31 P NMR (162MHz, CDCl3) δ 32.36 (s), -9.84 (s); HRMS (EI-TOF) m / z Calcd for C 78 H 110 O5P2Si[M] + : 1216.7598 found: 1216.7594.

[0967] Example 228: I-228

[0968]

[0969] White solid 1H NMR (400 MHz, CDCl3) δ 8.02 (dd, J = 6.8, 1.2 Hz, 1H), 7.72 (dd, J = 7.6, 1.2 Hz, 1H), 7.65 (t, J = 7.2 Hz, 1H), 7.61 (s, 4H), 7.55–7.48 (m, 1H), 7.31–7.27 (m, 1H), 7.24–7.17 (m, 1H), 7.10 (s, 4H), 3.82 (s,12H), 2.65–2.59 (m, 2H), 2.59–2.51 (m, 2H), 1.88–1.78 (m, 4H), 1.41 (d, J =1.6 Hz, 72H), 1.11–1.03 (m, 4H); 13 C NMR (100 MHz, CDCl3) δ 140.6, 139.3, 130.8, 129.5, 61.1, 37.7, 37.4, 35.00, 34.99, 30.5, 21.6, 12.0; 31 P NMR (162MHz, CDCl3) δ 32.36 (s), -9.84 (s); HRMS (EI-TOF) m / z Calcd for C 78 H 110 O5P2Si[M] + : 1216.7598 found: 1216.7600.

[0970] Application Example 1:

[0971]

[0972] Bis(dibenzylacetone)palladium (1.4 mg, 0.0025 mmol, 2.5 mol%), ligand (0.005 mmol, 5.0 mol%), VI-1 (0.1 mmol, 1.0 equiv), VII-1 (0.1 mmol, 1.0 equiv), and ultra-dry tert-amyl alcohol (1.0 mL) were added to a sealed tube. The catalytic system was stirred at room temperature for 30 min, followed by the addition of diisopropylethylamine (25.8 mg, 0.2 mmol, 2.0 equiv). The tube was then sealed and heated in a 70°C oil bath for 10 h. After the reaction was complete, the metal was removed by filtration through a short silica gel column, eluted with EA, and the resulting filtrate was evaporated to dryness. Then, CDCl3 and CH2Br2 (7.0 μL) were added, and the NMR yield was calculated by NMR. The effluent was determined by chiral HPLC.

[0973]

[0974]

[0975]

[0976]

[0977]

[0978]

[0979]

[0980]

[0981]

[0982]

[0983] Application Example 2:

[0984]

[0985] Bis(dibenzylacetone)palladium (1.4 mg, 0.0025 mmol, 2.5 mol%), ligand (0.005 mmol, 5.0 mol%), VI (0.1 mmol, 1.0 equiv), VII (0.1 mmol, 1.0 equiv), and ultra-dry tert-amyl alcohol (1.0 mL) were added to a sealed tube. The catalytic system was stirred at room temperature for 30 min, followed by the addition of diisopropylethylamine (25.8 mg, 0.2 mmol, 2.0 equiv). The tube was then sealed and heated in an oil bath at 70°C for 10 h. After the reaction was complete, the metal was removed by filtration through a short silica gel column, eluted with EA, and the resulting filtrate was evaporated to dryness. The yield was obtained by preparative plate separation, and ee was determined by chiral HPLC.

[0986] Following the above procedures and feeding methods, and using the corresponding raw materials, compounds VIII-1 to VIII-6 were obtained.

[0987] VIII-1

[0988]

[0989] White liquid. 82%, 93% ee. [chiral HPLC analysis (Chiralcel IC column (25cm), hexane / 2-propanol = 99 / 1; flow rate, 1.0 mL / min; 254 nm, t R (major) = 10.87 min; t R (minor) = 11.79 min], [α] D 33 = + 11.2 (c = 0.5, CHCl3); 1 1H NMR(400 MHz, CDCl3) δ 7.93 (d, J = 8.0 Hz, 2H), 7.74 (dd, J = 10.0, 8.0 Hz, 1H), 7.56 (t, J = 8.4, 6.8 Hz, 1H), 7.48 (d, J = 6.8 Hz, 2H), 7.41–7.30 (m, 2H), 7.28–7.22 (m, 2H), 7.14 (d, J = 16.0 Hz, 1H), 6.27 (d, J = 16.0 Hz, 1H), 3.58 (s, 3H); 13 13C NMR (100 MHz, CDCl3) δ 166.6, 142.6, 141.4, 136.5, 136.4, 134.0, 133.5, 131.6, 129.3, 128.8, 128.5, 127.6, 126.5, 126.1, 125.39, 125.36, 120.0, 51.5; HRMS (ESI-OTf) m / z Calcd for C 20 15 15 H9O2NaBr [M+Na] + : 389.0148, found: 389.0152。

[0990] VIII-2

[0991]

[0992] White solid. 78%, 84% ee. [chiral HPLC analysis (Chiralcel IBN-5 column(25 cm), hexane / 2-propanol = 99 / 1; flow rate, 1.0 mL / min; 254 nm, t R (major)= 11.62 min; t R (minor) = 15.05 min], [α] D 27 = + 75.4 (c = 0.53, CH2Cl2); 1 1H NMR (400 MHz, CDCl3) δ 8.03–7.92 (m, 4H), 7.58 (t, J = 7.2 Hz, 1H), 7.52 (d,J = 6.8 Hz, 1H), 7.41 (t, J = 7.2 Hz, 1H), 7.25 (d, J = 2.8 Hz, 2H), 7.20 (d,J = 8.4 Hz, 1H), 7.13 (d, J = 16.0 Hz, 1H), 6.34 (d, J = 16.0 Hz, 1H), 3.61(s, 3H); 19 19F NMR (375 MHz, CDCl3) δ -63.27; 13 13C NMR (100 MHz, CDCl3) δ 166.1,145.0, 141.2, 137.2, 135.2, 133.6, 131.7 (d, J = 33.7 Hz), 131.0, 130.4 (q, J= 3.8 Hz), 129.3, 128.7, 127.4, 126.9, 126.6, 126.4, 125.4, 124.9, 124.3,122.1 (q, J = 3.7 Hz), 121.8, 51.7. HRMS (ESI-OTf) m / z Calcd for C 21 H 14 O2F3NaBr[M+Na] + : 457.0022, found: 457.0020.

[0993] VIII-3

[0994]

[0995] White solid. 90%, 96% ee. [chiral HPLC analysis (Chiralcel IC column (25cm), hexane / 2-propanol = 99 / 1; flow rate, 1.0 mL / min; 254 nm, t R (major) = 13.22 min; t R (minor) = 14.96 min], [α] D 32 = -112.0 (c = 0.5, CHCl3); 1 1H NMR(400 MHz, CDCl3) δ 8.78 (dd, J = 11.2, 8.0 Hz, 2H), 7.90 (d, J = 7.6 Hz, 1H),7.81 – 7.75 (m, 2H), 7.75 – 7.62 (m, 3H), 7.56 (s, 1H), 7.49 (d, J = 7.6 Hz,1H), 7.38 (d, J = 8.0 Hz, 1H), 7.30 (d, J = 7.6 Hz, 1H), 7.26 (d, J = 16.0Hz, 1H), 6.33 (d, J = 16.0 Hz, 1H), 3.55 (s, 3H); 13 13C NMR (100 MHz, CDCl3) δ166.6, 142.5, 141.3, 136.6, 135.1, 134.1, 131.3, 130.6, 130.49, 130.45,129.4, 129.0, 128.7, 127.1, 127.0, 126.9, 126.8, 126.2, 126.1, 125.3, 123.1,122.7, 120.2, 51.6. HRMS (ESI-OTf) m / z Calcd for C 24 H 17 O2NaBr [M+Na] + : 439.0304,found: 439.0303.

[0996] VIII-4

[0997]

[0998] Colorless liquid. 58%, 93% ee. [chiral HPLC analysis (Chiralcel IC column (25cm), hexane / 2-propanol = 99 / 1; flow rate, 1.0 mL / min; 254 nm, t R (major) = 10.15 min; t R (minor) = 10.83 min], [α] D 27 = + 17.5 (c = 2.2, CH2Cl2); 1 1H NMR(400 MHz, CDCl3) δ 7.94 (d, J = 7.6 Hz, 2H), 7.75 (d, J = 6.8 Hz, 1H), 7.56(t, J = 7.2 Hz, 1H), 7.49 (t, J = 6.8 Hz, 1H), 7.43–7.33 (m, 2H), 7.30–7.22(m, 3H), 7.13 (d, J = 16.0 Hz, 1H), 6.28 (d, J = 16.0 Hz, 1H), 4.05 (d, J =7.2 Hz, 2H), 1.15 (d, J = 7.2 Hz, 3H); 13 13C NMR (100 MHz, CDCl3) δ 166.2,142.4, 141.5, 136.5, 136.4, 133.9, 133.5, 131.6, 129.3, 128.8, 128.5, 127.7,126.5, 126.1, 125.34, 125.31, 125.2, 120.4, 60.4, 14.1. HRMS (ESI-OTf) m / zCalcd for C 21 15H 17 O2NaBr [M+Na] + : 403.0304, found: 403.0314.

[0999] VIII-5

[1000]

[1001] Colorless liquid. 51%, 91% ee. [chiral HPLC analysis (Chiralcel IC column (25cm), hexane / 2-propanol = 90 / 10; flow rate, 1.0 mL / min; 254 nm, t R (major) = 24.32 min; t R (minor) = 27.24 min], [α] D 27 = + 15.2 (c = 1.5, CH2Cl2); 1 1H NMR(400 MHz, CDCl3) δ 7.93 (t, J = 7.2 Hz, 2H), 7.75 (d, J = 8.4 Hz, 1H), 7.70(d, J = 8.0 Hz, 1H), 7.56 (t, J = 7.2 Hz, 1H), 7.49 (t, J = 8.0 Hz, 1H), 7.36(dt, J = 15.6, 8.0 Hz, 2H), 7.30–7.22 (m, 3H), 7.01 (d, J = 15.6 Hz, 1H),6.21 (d, J = 16.0 Hz, 1H), 5.29 (s, 2H); 13 13C NMR (100 MHz, CDCl3) δ 167.0,141.2, 139.8, 136.7, 136.5, 133.7, 133.5, 131.5, 129.2, 128.8, 128.5, 127.7,126.5, 126.11, 126.08, 125.4, 125.3, 122.4, 29.7. HRMS (ESI-OTf) m / z Calcd forC 19 H 15 NOBr [M+H] + : 352.0332, found: 352.0339.

[1002] VIII-6

[1003]

[1004] White solid. 74%, 89% ee. [Chiral HPLC analysis (Chiralcel IC column (25cm), hexane / 2-propanol = 99.7 / 0.3; flow rate, 1.0 mL / min; 254 nm, t] R (major) = 16.0 min; t R (minor) = 17.14 min], [α] D 27 = + 135.2 (c = 0.55, CH2Cl2); 1 HNMR (400 MHz, CDCl3) δ 7.95 (dd, J = 8.4, 4.4 Hz, 2H), 7.82 (d, J = 7.6 Hz, 1H), 7.66 (d, J = 8.0 Hz, 1H), 7.58 (d, J = 7.2 Hz, 1H), 7.53–7.45 (m, 1H), 7.44–7.30 (m, 4H), 7.20–7.09 (m, 3H), 7.06 (d, J = 8.0 Hz, 2H), 6.97 (d, J =16.4 Hz, 1H), 6.52 (d, J = 16.0 Hz, 1H); 13 C NMR (100 MHz, CDCl3) δ 139.7,139.2, 137.4, 136.8, 133.5, 131.7, 131.5, 130.5, 129.1, 128.5, 128.33,128.30, 127.7, 126.8, 126.5, 126.4, 126.0, 125.7, 125.6, 125.4, 124.0. HRMS(EI) m / z Calcd for C 24 H 17 Br [M] + : 384.0517, found: 384.0508.

[1005] Application Example 3:

[1006]

[1007] In a glove box, bis(di-benzylacetone)palladium(0) (2.8 mg, 0.005 mmol, 5.0 mol%), ligand (0.01 mmol, 10 mol%), and dry tetrahydrofuran (1.0 mL) were added to a sealed tube. After stirring at room temperature for 30 min, VI-1 (0.1 mmol, 1.0 equiv), NEt3 (35.4 mg, 0.35 mmol, 3.5 equiv), and phenylacetylene (0.3 mmol, 3.0 equiv) were added. After stirring at room temperature for 5 min, CuI (0.01 mmol) was added. The sealed tube was then heated in a 70°C oil bath for 24 h. After the reaction was complete, the metal was removed by filtration through a short silica gel column, eluted with EA, and the resulting filtrate was evaporated to dryness. CDCl3 and CH2Br2 (7.0 μL) were then added, and the NMR yield was calculated by NMR, with ee determined by chiral HPLC.

[1008]

[1009]

[1010]

[1011] .

Claims

1. A compound as shown in Formula I or Formula II, ； in, n1, n2, n3, and n4 are independently 0, 1, 2, or 3; R 1 R 1’ R 6 and R 6’ Independently H, halogen, -N(R) 1a (R) 1b ), R 1c -L 1 -、C6-C 14 aryl, with one or more R 1g Replacement C6-C 14 aryl, 5-6 membered heteroaryl, or with one or more R 1h Substituted 5-6 heteroaryl; the 5-6 heteroaryl and one or more R 1h In the substituted 5-6-membered heteroaryl group, the number of heteroatoms in the heteroaryl group is independently 1-4, and the heteroatoms are selected from one or more of N, O and S; Alternatively, when n1, n2, n3, and n4 are independently 2 or 3, two adjacent R 1 and the C atom connected to it, and / or, the two adjacent R atoms 1’ and the C atom connected to it, and / or, the two adjacent R atoms 6 and the C atom connected to it, and / or, the two adjacent R atoms 6’ Together with the C atom attached thereto, it independently forms a C3-C7 cycloalkyl, a 5-6 membered heterocycloalkyl, or a phenyl; wherein the number of heteroatoms in the 5-6 membered heterocycloalkyl is independently 1-3, and the heteroatoms are selected from one or more of N, O, and S; R 1a and R 1b Independently H, C1-C8 alkyl, or C1-C8 alkyl-C(=O)-; R 1c Independently H, C1-C8 alkyl, or C1-C8 alkyl substituted with one or more halogens. , benzyl or benzyl or benzyl with one or more R 1i Substituted benzyl; L 1 Independently, it can be a linker, -O-, -C(=O)-, or -OC(=O)-; R 1d R 1e and R 1f It is independently a C1-C8 alkyl, C1-C8 alkyl-O-, phenyl, or is substituted by one or more R 1i Substituted phenyl; R 1g R 1h and R 1i Independently, it is a halogen, a C1-C8 alkyl group, a C1-C8 alkyl group substituted with one or more halogens, a C1-C8 alkyl-O-, a C1-C8 alkyl-C(=O)-, a C1-C8 alkyl-OC(=O)-, a C1-C8 alkyl-C(=O)-O-, a -NH2, a (C1-C8 alkyl-C(=O)-)NH-, a (C1-C8 alkyl-C(=O)-)2N-, or a C6-C 14 Aryl; R 2 R 2’ R 3 R 3’ R 7 R 7’ R 8 R 8’ R 9 and R 9’ Independently H, halogen, -N(R) 2a (R) 2b ), R 2c -L 2 -、C6-C 14 aryl, with one or more R 2g Replacement C6-C 14 aryl, 5-6 membered heteroaryl, or with one or more R 2h Substituted 5-6 heteroaryl; the 5-6 heteroaryl and one or more R 2h In the substituted 5-6 membered heteroaryl groups, the number of heteroatoms is independently 1-4, and the heteroatoms are selected from one or more of N, O and S; R 2a and R 2b Independently H, C1-C8 alkyl, or C1-C8 alkyl-C(=O)-; L 2 For connection keys, -O-, -C(=O)-, or -OC(=O)-; R 2c It is independently a C1-C8 alkyl or a C1-C8 alkyl substituted with one or more halogens; R 2g and R 2h Independently, it is a halogen, a C1-C8 alkyl group, a C1-C8 alkyl group substituted with one or more halogens, a C1-C8 alkyl-O-, a C1-C8 alkyl-C(=O)-, a C1-C8 alkyl-OC(=O)-, a C1-C8 alkyl-C(=O)-O-, a -NH2, a (C1-C8 alkyl-C(=O)-)NH-, or a (C1-C8 alkyl-C(=O)-)2N-; Or, R 2 and R 3 Connected, R 2’ and R 3’ Connected, R 7 and R 8 Connected, R 8 and R 9 Connected, R 7’ and R 8’ Connected, and / or R 8’ and R 9’ They are connected together with their C and C bonds to form C3-C7 cycloalkyl or phenyl groups; R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently, H, C1-C8 alkyl, C1-C8 alkyl substituted with one or more halogens, C1-C8 alkyl (C=O)-, C1-C8 alkyl (C=O)NH-, [C1-C8 alkyl (C=O)]2N-, nitro, cyano, 3-7 membered cycloalkyl, C6-C 15 aryl, 5-14 heteroaryl, or with one or more R 4d Replacement C6-C 15 Aryl; in the 5-14 membered heteroaryl groups, the number of heteroatoms is independently 1-4, and the heteroatoms are selected from one or more of N, O and S; R 4d Independently halogen, C1-C8 alkyl, C1-C8 alkyl-O-, C6-C 15 Aryl, -N(R) 4e (R) 4f ), nitro, cyano, or with one or more R 4i Replacement C6-C 15 aryl; wherein the C1-C8 alkyl and C1-C8 alkyl-O-, the C1-C8 alkyl is optionally surrounded by one or more elements selected from halogens or C6-C 14 Substitution of aryl groups; R 4e and R 4f Independently H or C1-C8 alkyl; R 4i Independently, it is a halogen, a C1-C8 alkyl group, a C1-C8 alkyl group substituted with one or more halogens, a C1-C8 alkyl-O-, a C1-C8 alkyl-C(=O)-, a C1-C8 alkyl-OC(=O)-, a C1-C8 alkyl-C(=O)-O-, a -NH2, a (C1-C8 alkyl-C(=O)-)NH-, or a (C1-C8 alkyl-C(=O)-)2N-; Or, R 4 and R 5 Connected, R 4’ and R 5’ Connected, R 10 and R 11 Connected, and / or R 10’ and R 11’ They are connected together with their C and C bonds to form C3-C7 cycloalkyl or phenyl groups; It indicates the chiral center, which is either S-configuration or R-configuration.

2. The compound as shown in Formula I or Formula II as claimed in claim 1, characterized in that, It satisfies at least one of the following conditions: (1) R 1 and R 1’ same; (2) R 2 and R 2’ same; (3) R 3 and R 3’ same; (4) R 4 and R 5 same; (5) R 4’ and R 5’ same; (6) R 6 and R 6’ same; (7) R 7 and R 7’ same; (8) R 8 and R 8’ same; (9) R 9 and R 9’ same; (10) R 10 and R 11 same; (11) R 10’ and R 11’ same; (12) R 1 R 1’ R 6 and R 6’ For H; (13) R 2 and R 2’ For H; (14) R 3 and R 3’ For H; (15) R 7 and R 7’ For H; (16) R 8 and R 8’ For H; (17) R 9 and R 9’ For H; (18)R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently C1-C8 alkyl, 3-7 membered cycloalkyl, C6-C 15 aryl, 5-14 heteroaryl, or with one or more R 4d Replacement C6-C 15 Aryl; in the 5-14 membered heteroaryl groups, the number of heteroatoms is independently 1-4, and the heteroatoms are selected from one or more of N, O and S; (19)R 4d Independently halogen, C1-C8 alkyl, C1-C8 alkyl-O-, C6-C 15 Aryl, -N(R) 4e (R) 4f ); wherein the C1-C8 alkyl group and the C1-C8 alkyl-O- group are optionally surrounded by one or more elements selected from halogens or C6-C 14 Substitution of aryl groups; (20)R 4e and R 4f It is independently a C1-C8 alkyl group.

3. The compound as shown in Formula I or Formula II as claimed in claim 2, characterized in that, It satisfies at least one of the following conditions: (1) When R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ When independently a C1-C8 alkyl group, the C1-C8 alkyl group is methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl, preferably isopropyl or tert-butyl; (2) When R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ When independently a 3-7 membered cycloalkyl group, the 3-7 membered cycloalkyl group is a 4-6 membered cycloalkyl group, preferably cyclobutyl, cyclopentyl or cyclohexyl, more preferably cyclohexyl; (3) When R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for C6-C 15 In the aryl case, the C6-C 15 The aryl group is C6-C. 10 Aryl, preferably phenyl or naphthyl; (4) When R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ When independently a 5-14 membered heteroaryl group, the 5-14 membered heteroaryl group is preferably a 5-10 membered heteroaryl group. , , or ; (5) When R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for one or more R 4d Replacement C6-C 15 In the aryl case, the C6-C 15 The aryl group is C6-C. 10 Aryl, preferably phenyl or naphthyl; (6) When R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for one or more R 4d Replacement C6-C 15 When aryl is used, the number of one or more is 1 to 7, preferably 1, 2 or 3; (7) When R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for one or more R 4d Replacement C6-C 15 Aryl, R 4d When the halogen is halogen, the halogen is F, Cl or Br, preferably F or Cl; (8) When R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for one or more R 4d Replacement C6-C 15 Aryl, R 4d When the alkyl group is C1-C8, the C1-C8 alkyl group is methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl, preferably methyl, isopropyl or tert-butyl; (9) When R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for one or more R 4d Replacement C6-C 15 Aryl, R 4d When the C1-C8 alkyl-O- is methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl, preferably methyl or isopropyl; (10) When R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for one or more R 4d Replacement C6-C 15 Aryl, R 4d For C6-C 15 In the aryl case, the C6-C 15 The aryl group is C6-C. 10 Aryl, preferably phenyl; (11) When R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for one or more R 4d Replacement C6-C 15 Aryl, R 4d The alkyl group is C1-C8, and when the C1-C8 alkyl group is substituted by one or more halogens, the halogens are F, Cl or Br, preferably F; (12) When R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for one or more R 4d Replacement C6-C 15 Aryl, R 4d The alkyl group is C1-C8, and when the C1-C8 alkyl group is replaced by one or more halogens, the one or more halogens are preferably three; (13) When R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for one or more R 4d Replacement C6-C 15 Aryl, R 4d It is a C1-C8 alkyl group, wherein the C1-C8 alkyl group is formed by one or more C6-C atoms. 14 When aryl is substituted, the C6-C 14 The aryl group is C6-C. 10 Aryl, preferably phenyl; (14) When R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for one or more R 4d Replacement C6-C 15 Aryl, R 4d It is a C1-C8 alkyl group, wherein the C1-C8 alkyl group is formed by one or more C6-C atoms. 14 When aryl substitution occurs, the C1-C8 alkyl group is methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl, preferably methyl; (15) When R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for one or more R 4d Replacement C6-C 15 Aryl, R 4d It is a C1-C8 alkyl group, wherein the C1-C8 alkyl group is formed by one or more C6-C atoms. 14 When aryl substitution is involved, one or more of the above is preferred; (16) When R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for one or more R 4d Replacement C6-C 15 Aryl, R 4d It is a C1-C8 alkyl-O-, wherein when the C1-C8 alkyl is substituted by one or more halogens, the halogen is F, Cl or Br, preferably F; (17) When R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for one or more R 4d Replacement C6-C 15 Aryl, R 4d The C1-C8 alkyl-O- is a C1-C8 alkyl group, wherein the C1-C8 alkyl group is substituted by one or more halogens, preferably three halogens; (18) When R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for one or more R 4d Replacement C6-C 15 Aryl, R 4d The C1-C8 alkyl-O- is a C1-C8 alkyl group. When the C1-C8 alkyl group is substituted by one or more halogens, the C1-C8 alkyl group is methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl, preferably methyl. (19) When R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for one or more R 4d Replacement C6-C 15 Aryl, R 4d It is a C1-C8 alkyl-O-, wherein the C1-C8 alkyl group is formed by one or more C6-C... 14 When aryl is substituted, the C6-C 14 The aryl group is C6-C. 10 Aryl, preferably phenyl; (20) When R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for one or more R 4d Replacement C6-C 15 Aryl, R 4d It is a C1-C8 alkyl-O-, wherein the C1-C8 alkyl group is formed by one or more C6-C... 14 When aryl substitution is involved, one or more of the above is preferred; (21) When R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for one or more R 4d Replacement C6-C 15 Aryl, R 4d It is a C1-C8 alkyl-O-, wherein the C1-C8 alkyl group is formed by one or more C6-C... 14 When aryl substitution occurs, the C1-C8 alkyl group is methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl, preferably methyl; (22) When R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for one or more R 4d Replacement C6-C 15 Aryl, R 4d -N(R) 4e (R) 4f ), R 4e and R 4f When independently a C1-C8 alkyl group, the C1-C8 alkyl group is methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl, preferably methyl.

4. The compound as shown in Formula I or Formula II as claimed in claim 2, characterized in that, R 4 R 4 '、R 5 R 5 '、R 10 R 10’ R 11 and R 11’ Independently for Cy, t Bu、 i Pr, Ph, , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , or .

5. The compound as shown in Formula I or Formula II according to any one of claims 1-4, characterized in that, The compound shown in Formula I is a compound shown in Formula Ia or Formula Ib; the compound shown in Formula II is a compound shown in Formula IIa or Formula IIb. ； Where, n1, n2, n3, n4, R 1 R 1 '、R 2 R 2 '、R 3 R 3’ R 4 R 4 '、R 5 R 5 '、R 6 R 6’ R 7 R 7 '、R 8 R 8 '、R 9 R 9’ R 10 R 10’ R 11 and R 11’ The definition is as described in any one of claims 1-4.

6. The compound as shown in Formula I or Formula II as claimed in claim 5, characterized in that, The compound represented by Formula I or Formula II has any of the following structures: 。 7. A catalyst composition comprising a metal complex formed by a compound of any one of claims 1-6, as shown in Formula I or Formula II, and a salt of a group 3 to 13 metal, and / or a mixture of a compound of any one of claims 1-6, as shown in Formula I or Formula II, and a reagent of a group 3 to 13 metal; Preferably, the group 3 to 13 metals are Pd or Rh, for example, Pd; the salts of the group 3 to 13 metals are Pd(OAc)2, Pd(dba)2 or Rh(acac)(CO)2, for example, Pd(dba)2. In the catalyst composition, the molar ratio of the compound as shown in Formula I or Formula II to the metals of Groups III to 13 is 1:1 to 4:1, for example 2:

1.

8. The use of a compound of formula I or formula II as described in any one of claims 1-6, or a catalyst composition as described in claim 7, in catalytic asymmetric organic synthesis reactions; In the aforementioned applications, the compounds represented by Formula I or Formula II serve as chiral ligands; Preferably, in the application described, the asymmetric organic synthesis reaction is a palladium-catalyzed asymmetric Sonogashira reaction and / or a palladium-catalyzed asymmetric Heck reaction; More preferably, in the application, the asymmetric organic synthesis reaction is a palladium-catalyzed asymmetric Sonogashira reaction for constructing axial chirality and / or a palladium-catalyzed asymmetric Heck reaction for constructing axial chirality.

9. A method for preparing a compound of formula I as described in any one of claims 1-6, characterized in that, It includes the following steps: In an organic solvent, in the presence of a palladium catalyst, a phosphine ligand, a base, and a disubstituted phosphine oxide, the compound shown in Formula V-1 is subjected to reaction 1 as shown below to give the compound shown in Formula I. ； Among them, R 1 R 1’ R 2 R 2’ R 3 R 3’ R 4 R 4’ R 5 R 5’ The definitions of n1 and n2 are as described in any one of claims 1-6; Preferably, the method for preparing the compound as shown in Formula I further includes the following steps: in an organic solvent, in the presence of trichlorosilane and a base, the compound as shown in Formula IV-1 is subjected to reaction 2 as shown below to obtain the compound as shown in Formula V-1. ； More preferably, the method for preparing the compound as shown in Formula I further includes the following steps: in an organic solvent, in the presence of a palladium catalyst, a phosphine ligand, a base and a disubstituted phosphine oxide, the compound as shown in Formula III-1 is subjected to reaction 3 as shown below to obtain the compound as shown in Formula IV-1. 。 10. The preparation method according to claim 9, characterized in that, It satisfies at least one of the following conditions: (1) In reaction 1, the organic solvent is one or more of ether solvents, haloalkanes solvents, aromatic solvents, nitrile solvents, alkane solvents, alcohol solvents, ketone solvents, amide solvents and sulfoxide solvents, preferably one or more of ether solvents, haloalkanes solvents, aromatic solvents and sulfoxide solvents, more preferably sulfoxide solvents; (2) In reaction 1, the palladium catalyst is one or more of palladium acetate, palladium chloride, palladium bromide, palladium iodide, palladium / carbon, palladium hydroxide, palladium oxide, palladium nitrate, palladium sulfate, ammonium chloropalladate, sodium chloropalladate, and potassium chloropalladate, preferably palladium acetate; (3) In reaction 1, the phosphine ligand is triphenylphosphine, trimethylphosphine, tricyclohexylphosphine, tri-tert-butylphosphine, di-tert-butylmethylphosphine, bis(dicyclohexylphosphine)methane, n-butyldi(1-adamantyl)phosphine, tri(p-tolyl)phosphine, tri(m-tolyl)phosphine, 2-(diphenylphosphino)-biphenyl, tri(3,5-xylyl)phosphine, tri(pentafluorophenyl)phosphine, tri(4-fluorophenyl)phosphine, tri(4-methoxyphenyl)phosphine, tri( 3-Methoxyphenyl)phosphine, tris(2,4,6-trimethoxyphenyl)phosphine, tris(4-trifluorotolyl)phosphine, tris[3,5-bis(trifluoromethyl)phenyl]phosphine, 2-diphenylphosphine-2'-methylbiphenyl, tris-2-furanylphosphine, diphenyl-2-pyridylphosphine, tris(2,6-dimethoxyphenyl)phosphine, diphenylmethylphosphine, tris(1-naphthyl)phosphine, cyclohexyldiphenylphosphine, dicyclohexylphenylphosphine, SPhos, XPhos t BuXPhos, DavePhos, BrettPhos, JohnPhos, MePhos, 2′-Dicyclohexylphosphine-2,4,6-trimethoxybiphenyl, RuPhos, PhDavePhos, 1,1′-bis(dicyclohexylphosphine)ferrocene, dppf, bis(diphenylphosphine)methane, 1,2-bis(biphenylphosphine)ethane, 1,3-bis(diphenylphosphine)propane, 1,4-bis(diphenylphosphine)propane One or more of the following: 1,8-bis(diphenylphosphine)octane, Cy-DPEPhos, DPEPHos, XantPhos, 2,2'-bis(dicyclohexylphosphine)-1,1'-biphenyl, BINAP, SEGPHOS, DTBM-SEGPHOS, cis-1,2-bis(diphenylphosphine)ethylene, and 2,6-bis(di-tert-butylphosphinemethyl)pyridine; preferably 1,4-bis(diphenylphosphine)butane; (4) In reaction 1, the base is an organic base or an inorganic base; the base is preferably N,N-diisopropylethylamine; (5) In reaction 1, the molar ratio of the compound shown in formula V-1 to the palladium catalyst is 30:1-5:1, more preferably 25:1-15:1; (6) In reaction 1, the molar ratio of the compound as shown in formula V-1 to the phosphine ligand is 30:1-5:1, more preferably 20:1-10:1; (7) In reaction 1, the molar ratio of the compound shown in formula V-1 to the base is 1:1-1:20, more preferably 1:2-1:3; (8) In reaction 1, the molar ratio of the compound shown in formula V-1 to the disubstituted phosphine oxygen is 1:1-1:10, more preferably 1:4-1:6; (9) In reaction 1, the molar concentration of the compound as shown in formula V-1 in the organic solvent is 0.05-1 mol / L, more preferably 0.1-0.5 mol / L; (10) The reaction 1 is carried out in the presence of an inert gas; the inert gas is preferably nitrogen or argon, more preferably nitrogen; (11) In reaction 2, the organic solvent is one or more of ether solvents, haloalkanes solvents, aromatic solvents, nitrile solvents, alkane solvents, alcohol solvents, ketone solvents, amide solvents and sulfoxide solvents, preferably aromatic solvents; (12) In reaction 2, the base is an organic base or an inorganic base; the base is preferably N,N-diisopropylethylamine; (13) In reaction 2, the molar ratio of the base to the compound shown in formula IV-1 is 300:1-10:1, more preferably 100:1-30:1, and even more preferably 100:1-70:1; (14) In reaction 2, the molar ratio of the trichlorosilane to the compound shown in formula IV-1 is 200:1-10:1, more preferably 50:1-20:1; (15) In reaction 2, the molar concentration of the compound as shown in formula IV-1 in the organic solvent is 0.01-4 mol / L, more preferably 0.05-2 mol / L, and even more preferably 0.1-0.3 mol / L; (16) In reaction 2, the temperature of the reaction is -20 to 200°C, more preferably 0 to 120°C; (17) The reaction 2 is preferably carried out in the presence of an inert gas; the inert gas is preferably nitrogen or argon, more preferably nitrogen; (18) In the reaction 3, the organic solvent is one or more of ether solvents, haloalkanes solvents, aromatic solvents, nitrile solvents, alkane solvents, alcohol solvents, ketone solvents, amide solvents and sulfoxide solvents, preferably one or more of ether solvents, haloalkanes solvents, aromatic solvents and sulfoxide solvents, more preferably sulfoxide solvents; (19) In reaction 3, the palladium catalyst is one or more of palladium acetate, palladium chloride, palladium bromide, palladium iodide, palladium / carbon, palladium hydroxide, palladium oxide, palladium nitrate, palladium sulfate, ammonium chloropalladate, sodium chloropalladate, and potassium chloropalladate; preferably palladium acetate; (20) In reaction 3, the phosphine ligand is triphenylphosphine, trimethylphosphine, tricyclohexylphosphine, tri-tert-butylphosphine, di-tert-butylmethylphosphine, bis(dicyclohexylphosphine)methane, n-butyldi(1-adamantyl)phosphine, tri(p-tolyl)phosphine, tri(m-tolyl)phosphine, 2-(diphenylphosphino)-biphenyl, tri(3,5-xylyl)phosphine, tri(pentafluorophenyl)phosphine, tri(4-fluorophenyl)phosphine, tri(4-methoxyphenyl)phosphine, tri( 3-Methoxyphenyl)phosphine, tris(2,4,6-trimethoxyphenyl)phosphine, tris(4-trifluorotolyl)phosphine, tris[3,5-bis(trifluoromethyl)phenyl]phosphine, 2-diphenylphosphine-2'-methylbiphenyl, tris-2-furanylphosphine, diphenyl-2-pyridylphosphine, tris(2,6-dimethoxyphenyl)phosphine, diphenylmethylphosphine, tris(1-naphthyl)phosphine, cyclohexyldiphenylphosphine, dicyclohexylphenylphosphine, SPhos, XPhos t BuXPhos, DavePhos, BrettPhos, JohnPhos, MePhos, 2′-Dicyclohexylphosphine-2,4,6-trimethoxybiphenyl, RuPhos, PhDavePhos, 1,1′-bis(dicyclohexylphosphine)ferrocene, dppf, bis(diphenylphosphine)methane, 1,2-bis(biphenylphosphine)ethane, 1,3-bis(diphenylphosphine)propane, 1,4-bis(diphenylphosphine)propane One or more of the following: 1,8-bis(diphenylphosphine)octane, Cy-DPEPhos, DPEPHos, XantPhos, 2,2'-bis(dicyclohexylphosphine)-1,1'-biphenyl, BINAP, SEGPHOS, DTBM-SEGPHOS, cis-1,2-bis(diphenylphosphine)ethylene, and 2,6-bis(di-tert-butylphosphinemethyl)pyridine; preferably 1,4-bis(diphenylphosphine)butane; (21) In reaction 3, the base is an organic base or an inorganic base; the base is preferably N,N-diisopropylethylamine; (22) In reaction 3, the molar ratio of the compound shown in formula III-1 to the palladium catalyst is 30:1-5:1, more preferably 25:1-15:1; (23) In reaction 3, the molar ratio of the compound as shown in formula III-1 to the phosphine ligand is 30:1-5:1, more preferably 20:1-10:1; (24) In reaction 3, the molar ratio of the compound as shown in formula III-1 to the base is 1:1-1:20, more preferably 1:2-1:3; (25) In reaction 3, the molar ratio of the compound shown in formula III-1 to the disubstituted phosphine oxygen is 1:1-1:5, more preferably 1:1-1:2; (26) In reaction 3, the molar concentration of the compound as shown in formula III-1 in the organic solvent is 0.05-1 mol / L, more preferably 0.05-0.2 mol / L; (27) The reaction 3 is preferably carried out in the presence of an inert gas; the inert gas is preferably nitrogen or argon, more preferably nitrogen.

11. A method for preparing a compound of formula II as described in any one of claims 1-6, characterized in that, It includes the following steps: in an organic solvent, in the presence of a palladium catalyst, a phosphine ligand, a base and a disubstituted phosphine oxide, the compound shown in Formula V-2 is reacted as shown in reaction 4 to obtain the compound shown in Formula II. ； Among them, R 6 R 6’ R 7 R 7’ R 8 R 8’ R 9 R 9’ R 10 R 10’ R 11 R 11’ The definitions of n3 and n4 are as described in any one of claims 1-6; Preferably, the method for preparing the compound shown in Formula II further includes the following steps: in an organic solvent, in the presence of trichlorosilane and a base, the compound shown in Formula IV-2 is subjected to reaction 5 as shown below to obtain the compound shown in Formula V-2. ； More preferably, the method for preparing the compound shown in Formula II further includes the following steps: in an organic solvent, in the presence of a palladium catalyst, a phosphine ligand, a base and a disubstituted phosphine oxide, the compound shown in Formula III-2 is subjected to the following reaction 6 to obtain the compound shown in Formula IV-2. ； Better, In reaction 4, the organic solvent, palladium catalyst, phosphine ligand, base, disubstituted phosphine oxide, and reaction conditions are any of the schemes in reaction 1 as described in claim 10; In reaction 5, the organic solvent, trichlorosilane, base, and reaction conditions are any of the schemes in reaction 2 as described in claim 10; In reaction 6, the organic solvent, palladium catalyst, phosphine ligand, base, disubstituted phosphine oxide, and reaction conditions are any of the schemes in reaction 3 as described in claim 10.

Images