Process for preparation of self-supported chiral catalyst polymers and catalyst polymers obtained thereby

Abstract

The present invention relates to a process for the preparation of self-supported chiral catalyst polymers via non-radical polymerization and the catalyst polymers thus obtained. A novel at least heterogeneous chiral catalyst readily obtainable via self-supported non-radical polymerization using a homogeneous chiral catalyst and optionally a homogeneous linker is disclosed. These heterogeneous chiral materials can be used as catalysts for different chemical conversions.

Description

[0001] This invention relates to a method for preparing self-supported chiral catalyst polymers via non-radical polymerization and the resulting catalyst polymers. The invention discloses a novel at least dimer heterogeneous chiral catalyst readily obtainable via self-supported non-radical polymerization using a homogeneous chiral catalyst and optionally a homogeneous linker. These heterogeneous chiral materials can be used as catalysts for various chemical transformations.

[0002] Since the concept of asymmetric organocatalysis was introduced two decades ago, it has gained widespread attention among chemists and has thus developed rapidly. Based on its fundamental activation modes (Lewis acids, Brønsted acids, Brønsted bases, and Lewis bases) and its numerous applications in a wide variety of chemical transformations, it has now become a major pillar of the field of asymmetric catalysis. Despite the development and progress of these catalysts, their application in technical processes is limited. One of the main reasons for their limited use as catalysts in industrial methods is the homogeneous nature of these catalysts, which requires additional separation steps and isolation to obtain their reusability. Typically, these operations are expensive, and potential catalyst loss has also been observed. To overcome this problem, heterogeneity of homogeneous chiral organocatalysts has been attempted, and moderate to good success has been achieved in some types of catalysts.

[0003] In the prior art, reactions for constructing polymer chains that optionally have chiral structural units are known.

[0004] For example, US 8067398 B2 discloses a method for preparing a self-supported chiral polymer, more specifically a method for preparing a biodegradable chiral polymer.

[0005] Similarly, Bor et al. disclosed (MACROMOLECULES (Vol. 26, No. 21, October 11, 1993, pp. 5664-5670) the preparation of chiral polymers that had no catalytic activity.

[0006] Itsuno Shinichi et al. disclosed, in only one example (POLYMER CHEMISTRY, Vol. 9 (2011-01-01), p. 1942), the preparation of a chiral catalyst in the form of a quaternary ammonium ion salt.

[0007] In JACS, Vol. 119 (May 1, 1997), pp. 4313-4314, Huang Wei-Sheng et al. describe a method for preparing polymeric ligands for metal catalysis. Such ligand-bonded metal catalysis leads to metal leaching, resulting in a loss of catalytic activity in the metal catalyst.

[0008] Furthermore, several attempts to prepare supported catalysts have been disclosed in the prior art. Reactions between functionalized homogeneous chiral catalysts and solid supports such as polystyrene polymers, fabrics, monoliths, etc. are disclosed in WO 2013-178640 A1, WO 2015-086793 A1 and WO 2017-08832 A1.

[0009] The free radical copolymerization of functionalized chiral homogeneous monomers with homogeneous achiral monomers is described in Tetrahedron 64 (2008) 1316-1322 and Advanced Synthesis & Catalysis 2010, 352, 281-287.

[0010] Oxidative radical self-polymerization of chiral homogeneous catalysts is disclosed in Advanced Synthesis & Catalysis 2011, 353, 3101-3106, Advanced Materials 2009, 21, 702-705; and Angew. Chem. Int. Ed. 2012, 51, 5456-5459.

[0011] The insoluble porous polymerization of homogeneous chiral basic organic catalysts is disclosed in Chemical Communications 2010, 46, 970-972.

[0012] The heterogeneous analogues of the known homogeneous catalysts have limited applications because of their specific types of activation modes, which significantly reduce the range of chemical transformations.

[0013] Another major problem is that their reactivity is significantly reduced compared to their homogeneous reactivity. The reason behind their low reactivity is:

[0014] a) The introduction of support materials (resin, fabric, etc.) leads to the dead volume of these catalysts;

[0015] b) Limited availability of active catalysts;

[0016] c) Overall catalyst structure and porosity.

[0017] To overcome reactivity limitations and broaden the range of different chemical transformations, this invention provides a novel strategy for heterogeneous transformation of known and unknown chiral homogeneous catalysts. Therefore, the heterogeneous materials can be used for asymmetric Brønsted acid / Lewis acid catalysis and / or asymmetric Brønsted base / Lewis base catalysis in various chemical transformations.

[0018] More specifically, the inventors have considered starting with known or unknown catalyst structural units (containing the desired functional groups) and optionally linking groups (containing the desired functional groups).

[0019] For illustrative purposes, the following scheme is used. In the concept of this invention, structural units may include the following formula, and the reactions between these structural units are schematically illustrated below:

[0020]

[0021] or

[0022]

[0023] or

[0024]

[0025] or

[0026]

[0027] or

[0028]

[0029] Using the structural unit shown as a platform molecule for the synthesis of self-supported heterogeneous catalysts has the following advantages:

[0030] a) The catalyst (C) is known and readily functionalized;

[0031] b) The linker (L) is readily available and also functionalizable;

[0032] c) All of the compounds mentioned have a finite dead volume, thus providing greater reactivity.

[0033] Therefore, this invention provides guidance for a more efficient and universal heterogeneous platform for a wide range of chiral organic catalysts.

[0034] As illustrated above, the present invention relates to a method for preparing a product containing (-C-ᴑ-C-ᴑ-). n Polymers of formula (III) or containing (–C-ᴑ-L-ᴑ-) nThe method of alternating polymers of formula (IV). Although it is generally feasible for the dimer of the reaction partner to act as a catalyst, it is preferred to repeat step b) of the method of the present invention several to hundreds of times to prepare a self-supported solid catalyst. In the polymers of formula (III) or (IV), the unit -ᴑ- represents a bond or group formed by the reaction of the reaction pair, which is selected from nucleophilic-electrophilic-reaction pairs or diene-dienophilic-reaction pairs. In a simple form, the unit -ᴑ- can be exemplary generated by the reaction of a nucleophilic group, such as -OH, on the catalyst molecule (C=Cat)HO-Cat-OH with an electrophilic group, such as O=(OR)CLC(OR)=O, which forms a group, such as HO-Cat-OC(=O)-LC(OR)=O, between the catalyst (C=Cat) and the linker group, and in a very simple form, the unit -ᴑ- can simply be the oxygen, such as -Cat-OL-, between the catalyst and the linker group.

[0035] More specifically, the present invention relates to a method for preparing a self-supported chiral catalyst polymer via non-radical polymerization, the method comprising the following steps:

[0036] a) Make equation (I) (X) 1 ) n -C-(X 2 ) m The compounds and those selected from formula (I) and formula (II) (X) 1 ) n -L-(X 2 ) m The compound reacts with the compound to form a dimer of the reacting compound, which contains at least one unit -ᴑ-, and optionally...

[0037] b) React the product of step a) with another compound selected from compounds of formula (I) and formula (II), thereby forming an oligomer of the reactant compound comprising at least two units -ᴑ-, and optionally...

[0038] c) Repeat step b) at least once, thereby forming an oligomer containing an additional unit -ᴑ- in each step b).

[0039] Where C represents a chiral catalyst, L represents a hydrocarbon linker, and X represents a hydrocarbon linker. 1 and X 2 The same or different, and the choice of compounds of formula (I) and formula (II) to represent reaction pairs, wherein the reaction pairs are selected from nucleophilic-electrophilic-reaction pairs or diene-dienophilic-reaction pairs, wherein

[0040] -ᴑ- indicates a unit in an oligomer chain formed by reactive chaperone pairs.

[0041] Wherein n and m independently represent integers ≥1, preferably 1-8, more preferably 1-4, even more preferably 1-2, and wherein the number of C in the polymer chain is preferably 2-100,000.

[0042] As schematically illustrated above, the reactive partners of a reaction pair react with each other to form polymer chains, which serve as polymer chains of catalyst units or as catalyst-linking copolymers. A pair of reactive partners typically reacts to form bonds between structural units, but the corresponding structural units may contain more than one reactive partner of the same type, such as several nucleophiles or several electrophiles, one or two of which typically react with the reactive partner, leaving one or more unreacted groups on the structural unit.

[0043] Those skilled in the art should understand that at the end of the reaction step, particularly due to the number of reactive groups on the reaction chaperone, the unreacted reaction chaperone X... 1 and X 2 It can exist on polymer chains without adversely affecting the catalytic performance of self-supported chiral catalysts, and can further react into non-reactive substances.

[0044] In another embodiment, the present invention relates to a method for preparing a self-supported chiral catalyst polymer via non-radical polymerization, the method comprising the following steps:

[0045] Make formula (I) (X) 1 ) n -C-(X 2 ) m The compound and formula (II) (X) 1 ) n -L-(X 2 ) m The compounds react in an organic solvent in the presence of a base for a sufficient time to complete the reaction between the compounds.

[0046] Where C represents a chiral catalyst, L represents a hydrocarbon linker, and X represents a hydrocarbon linker. 1 and X 2 The same or different, and the choice of each compound of formula (I) and formula (II) to represent the reaction pair, wherein the reaction pair is selected from nucleophilic-electrophilic-reaction pair or diene-dienophilic-reaction pair.

[0047] The reaction is typically carried out in a solvent, preferably an organic solvent, optionally in combination with water, in the presence of a base for a sufficient time to complete the polymerization process, which is usually achieved in a time range of up to 96 hours, sometimes depending on the reactants, and in a shorter time range of up to 48 hours or even up to 24 hours.

[0048] In a preferred embodiment of the latter, the present invention relates to a method for preparing a self-supported chiral catalyst polymer via non-radical polymerization, wherein formula (I) (X) 1 ) n -C-(X 2 ) m The compound and formula (II) (X) 1 ) n -L-(X 2 ) m The reaction of the compound is as shown in formula (I) (X) 1 ) n -C-(X 2 ) m The compound and formula (II) (X) 1 ) n -L-(X 2 ) m The compounds are carried out in a stoichiometric ratio of 1:1 to 1:10, preferably 1:2 to 1:6.

[0049] Those skilled in the art should also understand that at the end of the reaction step, a polymer of incalculable size is formed. During polymer formation, typically thousands of structural units bond to each other, and the reaction stops when the reactive groups X1 and X2 cease to react. At the end of the reaction, a solid polymer is formed and can be used to catalyze the desired reaction without any significant loss of activity over hundreds of reaction cycles.

[0050] According to the invention, a catalyst molecule having more than two electrophilic groups (e.g., three or four electrophilic groups) can react with another catalyst or linker molecule (having two nucleophilic groups), which in a first step produces a dimer with unreacted electrophilic groups, which reacts with another catalyst or linker molecule in a next step. Therefore, the invention also includes reacting the structural unit having more than one reactive group with a reaction chaperone having one or more reactive groups. In any case, the reaction chaperone of the reaction chaperone pair exists as a substituent on the catalyst, preferably far from the catalytic center so as not to significantly affect the catalytic activity, or exists on a hydrocarbon linker, preferably on its opposite hydrocarbon chain end.

[0051] Although dimers of reaction chaperones can generally be used as catalysts, it is preferred to repeat step b) of the method of the present invention several to hundreds of times to prepare a self-supported solid catalyst.

[0052] Therefore, in the method of this invention, the self-supported catalyst can be in a simple form comprising a dimer of catalyst structural units or a heterodimer of catalyst and linker groups, the solubility and loading capacity of which depend on the type and degree of substitution of the structural units. Depending on the type of reaction partners, the reaction between the structural units is either a substitution reaction between a nucleophile and an electrophile or a cycloaddition reaction, the latter forming a cyclic structural unit between the reaction partners. The products of both reaction pathways are included in the illustrations of formulas (III) and (IV).

[0053] In one embodiment of the method for preparing a self-supported chiral catalyst polymer via non-radical polymerization of the present invention, if the compound of formula (I) is similar to X of formula (II) 1 -LX 2 The reaction of the compound with formula (I) then the X on the compound. 1 and X 2 Each is a partner of a nucleophilic-electrophilic-reaction pair, and X on the compound of formula (II) 1 and X 2 Each is the corresponding partner of a nucleophilic-electrophilic-reaction pair, or

[0054] If equation (I) X 1 -CX 2 Compound X and another compound of formula (I) 1 -CX 2 The reaction then occurs on the X of the compound of formula (I). 1 It is a companion of the nucleophilic-electrophilic-reaction pair, and X on the compound of formula (I). 2 It is the corresponding partner of the nucleophile-electrophile-reaction pair.

[0055] In another embodiment of the method for preparing a self-supported chiral catalyst polymer via non-radical polymerization of the present invention, if the compound of formula (I) is similar to that of formula (II) X 1 -LX 2 In the reaction of compounds, X1 and X2 on the compound of formula (I) are each a partner of a diene-dienophile-reaction pair, and X1 and X2 on the compound of formula (II) are each a corresponding partner of a diene-dienophile-reaction pair, or

[0056] If equation (I) X 1 -CX 2 Compound X and another compound of formula (I) 1-CX 2 The reaction then occurs on the X of the compound of formula (I). 1 It is a partner of the diene-dienophile-reaction pair, and X on the compound of formula (I). 2 It is the corresponding partner of the diene-dienophile-reaction pair.

[0057] Although according to the present invention, the method of the present invention forms a structure containing (-C-ᴑ-C-ᴑ-). n Polymers of formula (III) or containing (–C-ᴑ-L-ᴑ-) n Alternating polymers of formula (IV) are feasible, but those containing (–C-ᴑ-L-ᴑ-) are not. n Polymers of formula (IV) are particularly important. They depend on formula (I) (X) 1 ) n -C-(X 2 ) m The compound and formula (II) (X) 1 ) n -L-(X 2 ) m The molar ratio of the compounds may favor the formation of oligomers or polymers with more L-structural units than Cat- in the polymer chain, because the catalytic centers are more widely spaced and can catalyze the reaction without any steric influence. Therefore, formula (I) (X) is preferred. 1 ) n -C-(X 2 ) m The compound and formula (II) (X) 1 ) n -L-(X 2 ) m The stoichiometric ratios of the compounds are 1:1 to 1:10 or greater. In practice, formulas (I) (X) in the range of 1:2 to 1:6 are more common. 1 ) n -C-(X 2 ) m The compound and formula (II) (X) 1 ) n -L-(X 2 ) m The stoichiometric ratio of the compounds results in satisfactory results in catalytic reactions using such self-supported catalysts. In this case, the polymer chain will contain the catalytically active substance C, which is separated or spaced from the nearest catalytically active substance C by several linking units, thus statistically forming exemplary sequences such as..–CLLLLLCLLLLLLLC-….

[0058] If in a certain case, equation (I) (X) 1 ) n -C-(X 2 ) m Compounds or formula (II) (X) 1 ) n -L-(X 2 ) m If a compound has more than one or two X1 or X2, then the stoichiometric ratio may be in the same range as given above.

[0059] According to the present invention, catalyst compound (X) 1 ) n -C-(X 2 ) m Preferred are phosphoramide imine compounds represented by the following general formula (VI), used to construct oligomers or polymer chains containing n(X) 1 ) n and m(X) 2 ) m Compounds of formula (VI) with the group described above.

[0060] In one embodiment of the invention, the nucleophilic group is preferably selected from -OH, -SH, -NHR, -B(OR)2, -SiR3, -OSiR3, -NRSiR3, -MgT, -ZnT, -SnR3, -Li, -Na, -PR2, -CO2 - -CHZ2, -CHRZ, -CR=PR3, -C≡CH, -CR=CHR, -C(OSiR3)=CR2, -CR=C(OSiR3)(OR), -CR2=CHR-CR2-SiR3, -C≡N=O, -CR=NR=O, where T represents a halogen, preferably Cl, Br, or I, and Z can be the same or different, and represents an electron-withdrawing group such as OTf, OTs, ONs, OMs, -CH=O, -CR=O, -C(OH)=O, -C(OR)=O, -NO2, -SO2R, or -CN, where R can be the same or different, and represents H, C1-C 20 Straight-chain, branched, or cyclic aliphatic hydrocarbons, C3-C8 heterocyclic alkyl hydrocarbons, C6-C 20 Aromatic hydrocarbons or their partially hydrogenated aromatic forms, or C5-C 19 Mixed aromatic hydrocarbons.

[0061] In one embodiment of the method of the present invention, the electrophilic group is preferably selected from H, F, Br, Cl, I, CN, NO2, -NR2, OTf, OTs, ONs, OMs, -CH=O, -CR=O, -C(OH)=O, -C(OR)=O, O=CR-O-RC=O, -C(Cl)=O, -C(Br)=O, -C(F)=O, -C(NR2)=O, -N=C=O, -N=C=S, -N=C=NR, -CR2Z, wherein R can be the same or different, and represents H, Cl-C 20 Straight-chain, branched, or cyclic aliphatic hydrocarbons, C3-C8 heterocyclic alkyl hydrocarbons, C6-C 20 Aromatic hydrocarbons or their partially hydrogenated aromatic forms, or C5-C 19 Heteroaromatic hydrocarbons, and Z indicates C2-C8 heterocyclic alkyl hydrocarbons.

[0062] Preferably, the reaction pair of the nucleophile and electrophile groups includes at least one nucleophile selected from the following: -OH, -SH, -NHR, -B(OR)2, or -CO2. - And at least one electrophilic group selected from the following: F, Br, Cl, I, or CN. The reaction can be promoted by using a base such as NaH or Na2CO3, and the reaction can proceed until the reactive group is consumed or the reaction no longer occurs due to steric conditions.

[0063] In one embodiment of the method of the present invention, the diene is a diene substituent -RC=CR-CR=CR2, wherein R can be the same or different, and represents H, C1-C 20 Straight-chain, branched, or cyclic aliphatic hydrocarbons, C3-C8 heterocyclic alkyl hydrocarbons, C6-C 20 Aromatic hydrocarbons or their partially hydrogenated aromatic forms, or C5-C 19 Mixed aromatic hydrocarbons.

[0064] In one embodiment of the method of the present invention, the dienophile is preferably a dienophile substituent -CR=CR2, wherein R can be the same or different, and represents H, C1-C 20 Straight-chain, branched, or cyclic aliphatic hydrocarbons, C3-C8 heterocyclic alkyl hydrocarbons, C6-C 20 Aromatic hydrocarbons or their partially hydrogenated aromatic forms, or C5-C 19 A heteroaromatic hydrocarbon, wherein at least one R has an electron-withdrawing group selected from the following: OTf, OTs, ONs, OMs, -CH=O, -CR=O, -C(OH)=O, -C(OR)=O, -NO2, -SO2R or -CN.

[0065] In one embodiment of the method of the present invention, the hydrocarbon linker L is preferably selected from C1-C1. 20Straight-chain, branched, or cyclic aliphatic hydrocarbons, C3-C8 heterocyclic alkyl groups, C6-C 20 Aromatic hydrocarbons or their partially aromatic hydrogenated forms, and C2-C 19 Heteroaromatic hydrocarbons, particularly those selected from C1-C groups having n and m, preferably 1-4, more preferably 1 or 2 X1 and X2 reactive groups, preferably -OH or -SH groups. 20 Straight-chain aliphatic hydrocarbons or C6-C 20 Aromatic hydrocarbons such as 4,4'-dihydroxybiphenyl or similar aromatic or aliphatic dihydroxy compounds.

[0066] In one embodiment of the method of the present invention, catalyst C is a chiral phosphoramide imine compound of general formula (V):

[0067]

[0068] in:

[0069] Y 1 and Y 2 O or NR can be represented independently of each other. N ,

[0070] W is preferably selected from hydrogen, halogens, and metal or cationic organic groups selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Mo, Ru, Rh, Pd, Ag, W, Re, Os, Ir, Pt, Au, Al, Pb, La, Sm, Eu, Yb, U, or substituted silicon-SiR I R II R III , where R I R II and R III Same or different, and each represents hydrogen, halogen, C1-C. 20 Straight-chain, branched, or cyclic aliphatic hydrocarbons, C3-C8 heterocyclic alkyl groups, C6-C 20 Aromatic hydrocarbons or their partially hydrogenated aromatic forms, or C5-C 19 heteroaromatic hydrocarbons

[0071] R 1 R 2 R 3 and R 4 They may be independently identical or different from each other, and each is an aliphatic, heteroaliphatic, aromatic, or heteroaromatic hydrocarbon group, each optionally further substituted with one or more of the following: heterosubstituents, aliphatic, heteroaliphatic, aromatic, or heteroaromatic hydrocarbon groups.

[0072] Where R 1 Can be used with R 2R 3 Or R 4 Any of them forms a ring system, and R 2 R 3 Or R 4 The other two in the system can form a ring system with each other; and

[0073] R N It is an electron-withdrawing group, and is the same or different for each N, and is selected from:

[0074] -alkyl, -CO-alkyl, -(CO)-O-alkyl, sulfinylalkyl, sulfonylalkyl, -(P=O)-dialkyl, wherein the alkyl group is C1-C 20 Straight-chain, branched, or cyclic aliphatic hydrocarbons having at least one halogen substituent on an alkyl residue, preferably F and / or Cl substituents;

[0075] Aryl, -CO-aryl, -(CO)-O-aryl, sulfinylaryl, sulfonylaryl, -(P=O)-diaryl, wherein the aryl group is C6-C 18 Aromatic hydrocarbons, preferably having at least one halogen substituent on an aryl residue, preferably F and / or Cl substituents;

[0076] Heteroaryl, -CO-heteroaryl, -(CO)-O-heteroaryl, sulfinylheteroaryl, sulfonylheteroaryl, -(P=O)-diheteroaryl, wherein the heteroaryl group is C2-C 20 Aromatic hydrocarbons, preferably having at least one halogen substituent on a heteroaryl residue, preferably F and / or Cl substituents;

[0077] Or its tautomerism or ionic form.

[0078] In another embodiment of the method of the present invention, catalyst C is a phosphoramide imine compound of general formula (V), wherein (R 1 and R 2 ) and (R 3 and R 4 Each ring system forms the same or different ring structures and is derived from a bridged, optionally dimer, aromatic structure selected from optionally substituted biphenyls, BINOL, TADDOL, VAPOL, SPINOL, 1,1'-binaphthyl, 1,1'-biphenanthrene, or a partially aromatic hydrogenated form of such an aromatic ring structure including 8H-BINOL. Each ring system is optionally substituted with one or more substituents, which are the same or different at each position, and each is selected from hydrogen, heterosubstituents, C1-C1 substituents. 20 Straight-chain, branched, or cyclic aliphatic hydrocarbons, C3-C8 heterocyclic alkyl groups, C6-C 20 Aromatic hydrocarbons or their partially hydrogenated aromatic forms, or C5-C19 heteroaromatic hydrocarbons

[0079] Among them, (R) 1 and R 2 ) and (R 3 and R 4 The ring structures formed are the same or different, and

[0080] Where Y 1 Y 2 As defined above, W

[0081] Or its tautomers or ionic forms.

[0082] According to the present invention, catalyst compound (X) 1 ) n -C-(X 2 ) m Preferably, the compounds are phosphoramide imine compounds represented by the following general formula (VI), wherein the compounds of formula (VI) have n (X) groups. 1 ) and m (X) 2 () groups are used to construct oligomers or polymer chains, where X1, X2, n, and m have the same meaning as given above.

[0083] In a more detailed embodiment of the method of the present invention, catalyst C is a phosphoramide imine compound of general formula (VI):

[0084]

[0085] In formula (IV), the substituent R is the same or different at each position, and each is selected from hydrogen, heterosubstituents, C1-C... 20 Straight-chain, branched, or cyclic aliphatic hydrocarbons, C3-C8 heterocyclic alkyl groups, C6-C 20 Aromatic hydrocarbons or their partially hydrogenated aromatic forms, or C5-C 19 heteroaromatic hydrocarbons, and Y 1 Y 2 And W as defined above, or its tautomer or ionic form. Any substituent R itself may carry other substituents, such as C1-C. 20 Optionally substituted aliphatic hydrocarbons, heterosubstituents, especially halogens and others.

[0086] In one specific embodiment of the method of the present invention, the nucleophilic-electrophilic-reaction pair comprises at least one fluorinated—partially or completely—C6-C—on the catalyst or linker side. 20 Aromatic hydrocarbons, and the reaction companion is an aliphatic or aromatic diol compound, such as a bisphenol compound as a companion.

[0087] In another embodiment of the method of the present invention, catalyst C is a phosphoramide imine compound represented by general formula (VII):

[0088]

[0089] The substituent R may be the same or different at each position, and each is selected from hydrogen, heterosubstituents, C1-C. 20 Straight-chain, branched, or cyclic aliphatic hydrocarbons, C3-C8 heterocyclic alkyl groups, C6-C 20 Aromatic hydrocarbons or their partially hydrogenated aromatic forms, or C5-C 19 heteroaromatic hydrocarbons

[0090] Y 1 Y 2 W as defined above, or its tautomerism or ionic form.

[0091] In another embodiment of the method of the present invention, catalyst C is selected from...

[0092]

[0093] In the formula, the substituent R is the same or different at each position, and each is selected from hydrogen, heterosubstituents, C1-C... 20 Straight-chain, branched, or cyclic aliphatic hydrocarbons, C3-C8 heterocyclic alkyl groups, C6-C 20 Aromatic hydrocarbons or their partially hydrogenated aromatic forms, or C5-C 19 Heteroaromatic hydrocarbons, and W as defined above, or their tautomers or ionic forms.

[0094] The present invention also relates to self-supported chiral catalyst polymers, which can be obtained by any of the methods defined above, and their use in organic synthesis.

[0095] The preferred use of the self-supported chiral catalyst polymer of the present invention is as a chiral catalyst in organic synthesis, wherein the synthetic reaction is selected from aldol reactions, intercalation aldol reactions, Mukaiyama aldol reactions, intercalation Mukaiyama aldol reactions, Mukaiyama-Michael reactions, Michael addition, Mannich reactions, TMSCN addition to aldehydes and ketones to imines, esterification, etherification, pinacol rearrangement, acetalization, transfer acetalization, spiroacetalization and related reactions, cycloaddition, hydroamylation, hydroalkoxylation, hydration, halogenation, etc. Alkoxylation, haloamination, olefin activation (usually including alkene reactions and Prince reactions), Friedel-Crafts reaction, epoxide ring opening, Ritter reaction, nucleophilic substitution of alcohols, asymmetric ring opening, asymmetric reduction, transfer hydrogenation, alkyne addition, imine addition, Strecker reaction, allylation, propargylation, reduction, epoxidation, olefin metathesis, isomerization, Diels-Alder reaction, hetero-Diels-Alder reaction, aminational amination, imine-onium catalysis, and enamine catalysis.

[0096] In the method of this invention, the choice of solvent is not critical and depends on the reaction partners. The solvent can be an aprotic, nonpolar organic solvent selected from diethyl ether, aromatic solvents such as benzene and toluene, aliphatic hydrocarbon solvents having 5-8 carbon atoms such as pentane, hexane, or mixtures thereof, or any other solvent such as DMSO, AMF, or THF, optionally combined with water, acetonitrile, and other solvents that will not adversely affect the polymerization reaction. Reaction conditions are also not critical, and the reaction is typically carried out at temperatures between 0°C and 300°C, preferably between 10°C and 150°C, under ambient pressure, preferably in an inert gas atmosphere.

[0097] The method of the present invention for preparing self-supported chiral catalyst polymers via non-radical polymerization preferably uses a base such as NaH, KH, CaH2, KOBut, LiHMDS, LDA, LiTMP, Mg(TMP)2, Zn(TMP)2, Ba(OH)2, K2CO3, NaOAc, Ag2CO3, Et3N, iPr2NEt, K3PO4, DBU or similar bases, depending on the reaction partner.

[0098] In the context of this invention, the meanings are as defined below. Hydrocarbons are preferably selected from C1-C6. 20 Straight-chain, branched, or cyclic aliphatic hydrocarbons, C3-C8 heterocyclic alkyl groups, C6-C 20 Aromatic hydrocarbons and some of their hydrogenated forms, or C5-C... 19 Mixed aromatic hydrocarbons.

[0099] The C1-C 20Alkyl groups preferably refer to straight-chain or branched alkyl groups having 1-20 carbon atoms, which may optionally be substituted with one or more electron-withdrawing groups, such as OTf, OTs, ONs, OMs, -CH=O, -CR=O, -C(OH)=O, -C(OR)=O, -NO2, -SO2R or -CN.

[0100] 5-19 membered heteroaromatic hydrocarbons, or simply heteroaryl, represent monocyclic or optionally bicyclic aromatic heterocycles (heteroaromatics) having a total of 5-10 ring atoms, containing up to three cyclic heteroatoms selected from the N, O, and / or S series, and linked via a cyclic carbon atom or optionally via a cyclic nitrogen atom. Examples are: furanyl, pyrroleyl, thiopheneyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl, isoxazolyl, isothiazolyl, triazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrazinyl, triazinyl, benzofuranyl, benzothiopheneyl, benzimidazolyl, benzooxazolyl, benzothiazolyl, benzotriazolyl, indolyl, inazolyl, quinolinyl, isoquinolinyl, naphridinyl, quinazolinyl, quinoxolinyl, phthalazinyl, pyrazolo[3,4-b]pyridinyl.

[0101] The heteroatom or heterosubstituent defined according to the present invention may be selected from OH, halogens, CN, NO2, NO, NCO, -NCS, -SCN, SO3H, monohalomethyl, dihalomethyl, trihalomethyl, CF(CF3)2, SF5, aliphatic, aromatic, heteroaromatic, primary, secondary, tertiary amines or ammonium compounds bonded through an N atom, -O-alkyl (alkoxy), -O-aryl, -O-heteroaryl, -O-SiR S 3, -SSR S -SR S , -S(O)-R S , -S(O)2-R S -COOH, -CO2-R S -BR S 2, -PR S 2, -OPR S 2. Amide (bonded via C or N atoms), formyl group, -C(O)-R S , -COOM, where M is a metal, such as Li, Na, K, Cs, Ag. R S They may be identical or different from each other independently, and each is an aliphatic, heteroaliphatic, aromatic, or heteroaromatic group, each optionally further substituted with one or more heterosubstituents, aliphatic, heteroaliphatic, aromatic, or heteroaromatic groups; and / or optionally bridged by -O- atoms, indicating a halide. In the context of this invention, halogen refers to fluorine, chlorine, bromine, and iodine.

[0102] When listing a range of values, the goal is to include every value within that range and its subranges. For example, "C 1–6The goal is to include C1, C2, C3, C4, C5, C6, C 1–6 C 1–5 C 1–4 C 1–3 C 1–2 C 2–6 C 2–5 C 2–4 C 2–3 C 3–6 C 3–5 C 3–4 C 4–6 C 4–5 and C 5–6 .

[0103] In the context of this invention, preferred alkyl groups are straight-chain or branched alkyl groups having 1-6 carbon atoms. Exemplary and preferred are: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 1-ethyl-propyl, n-pentyl, and n-hexyl.

[0104] In the context of this invention, preferred cycloalkyl groups are those having 3-7 carbon atoms. Exemplary and preferred are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl.

[0105] In the context of this invention, preferred cycloalkoxy groups are those having 3-7 carbon atoms. Exemplary and preferred examples are cyclopropoxy, cyclobutoxy, cyclopentoxy, cyclohexyloxy, and cycloheptoxy.

[0106] In the context of this invention, preferred di-C1-C4 alkylamino groups are the following di-C1-C4 alkylamino groups: N,N-dimethylamino, N,N-diethylamino, N-ethyl-N-methylamino, N-methyl-N-n-propylamino, N-isopropyl-N-methylamino, N-isopropyl-N-ethylamino, N-isopropyl-N-n-propylamino, N,N-diisopropylamino, N-n-butyl-N-methylamino, and N-tert-butyl-N-methylamino.

[0107] "Aryl" refers to a group in a monocyclic or polycyclic (e.g., bicyclic or tricyclic) 4n+2 aromatic ring system (e.g., having 6, 10, 14, 18, or 22 π electrons shared in the ring array), which provides 6-20 ring carbon atoms and zero heteroatoms ("C") in the aromatic ring system. 6-20 Aryl group (“C6 aryl”). In some embodiments, the aryl group has six ring carbon atoms (“C6 aryl”, e.g., phenyl). In some embodiments, the aryl group has ten ring carbon atoms (“C6 aryl”). 10 "Aryl"; for example, naphthyl (e.g., 1-naphthyl and 2-naphthyl). In some embodiments, the aryl group has fourteen cyclic carbon atoms ("C"). 14"Aryl"; for example, anthracene. "Aryl" also includes cyclic systems in which the aryl ring as defined above is fused with one or more carbocyclic or heterocyclic groups, wherein the linking group or linking point is located on the aryl ring, and in this case, the number of carbon atoms continues to represent the number of carbon atoms in the aryl ring system. Unless otherwise stated, the aryl group is optionally independently substituted in each case, i.e., unsubstituted ("unsubstituted aryl") or substituted with one or more substituents ("substituted aryl"). In some embodiments, the aryl group is an unsubstituted C 6-14 Aryl. In some embodiments, the aryl group is a substituted C. 6-14 Aryl.

[0108] 6-20 aryl groups typically represent monocyclic, bicyclic, or tricyclic carbocyclic aryl groups, which may further include 0-5 substituents selected from the following: C1-C12 alkyl, C1-C12 alkoxy, di-C1-C4 alkylamino, C3-C12 cycloalkyl, C3-C12 cycloalkoxy, 6-18 aryl, 5-10 heteroaryl, halogen, cyano, and nitro.

[0109] Preferred aryl groups in the context of this invention are: phenyl, naphthyl, anthracene, methylphenyl, dimethylphenyl, trimethylphenyl, methoxyphenyl, dimethoxyphenyl, trimethoxyphenyl, fluorophenyl, chlorophenyl, bromophenyl, iodophenyl, pentafluorophenyl, perfluoronaphthyl; trifluoromethylphenyl, dimethylaminophenyl, C1-C12 alkoxycarbonylphenyl.

[0110] "Aryl" is a subset of alkyl and aryl, referring to an alkyl group that is optionally substituted with an aryl group. In some embodiments, the aryl group is an optionally substituted benzyl group. In some embodiments, the aryl group is a benzyl group. In some embodiments, the aryl group is an optionally substituted phenethyl group. In some embodiments, the aryl group is a phenethyl group.

[0111] 5-19 membered heteroaromatic hydrocarbons, or simply heteroaryl, represent monocyclic or optionally bicyclic aromatic heterocycles (heteroaromatics) having a total of 5-10 ring atoms, containing up to three cyclic heteroatoms selected from the N, O, and / or S series, and linked via a cyclic carbon atom or optionally via a cyclic nitrogen atom. Examples are: furanyl, pyrroleyl, thiopheneyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl, isoxazolyl, isothiazolyl, triazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrazinyl, triazinyl, benzofuranyl, benzothiopheneyl, benzimidazolyl, benzooxazolyl, benzothiazolyl, benzotriazolyl, indolyl, inazolyl, quinolinyl, isoquinolinyl, naphridinyl, quinazolinyl, quinoxolinyl, phthalazinyl, pyrazolo[3,4-b]pyridinyl.

[0112] "Heteroaryl" refers to a 5-20 member monocyclic or bicyclic 4n+2 aromatic ring system (e.g., having 6, 10, 14, or 18 π electrons shared in a cyclic array) having a cyclic carbon atom and 1-4 cyclic heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur ("5-14 member heteroaryl"). In heteroaryls containing one or more nitrogen atoms, the linkage can be a carbon or nitrogen atom, provided the valence allows. Heteroaryl bicyclic systems may include one or more heteroatoms in one or both rings. "Heteroaryl" includes cyclic systems in which the heteroaryl ring as defined above is fused with one or more carbocyclic or heterocyclic groups, wherein the linkage is located on the heteroaryl ring, in which case the number of ring members continues to indicate the number of ring members in the heteroaryl cyclic system. "Heteroaryl" also includes ring systems in which a heteroaryl ring as defined above is fused with one or more aryl groups, wherein the linking point is located on either the aryl or heteroaryl ring. In this case, the number of ring members indicates the number of ring members in the fused (aryl / heteroaryl) ring system. In a bicyclic heteroaryl ring (e.g., indolyl, quinolinyl, carbazolyl, etc.) without a heteroatom in the ring, the linking point can be located on either ring, i.e., a ring with a heteroatom (e.g., 2-indolyl) or a ring without a heteroatom (e.g., 5-indolyl).

[0113] 5-10 membered heteroaryl groups generally represent monocyclic or optional bicyclic aromatic heterocycles (heteroaromatics) having a total of 5-10 ring atoms, containing up to three cyclic heteroatoms selected from the N, O, and / or S series, and linked via a ring carbon atom or optionally via a ring nitrogen atom. Examples are: furanyl, pyrroloyl, thiopheneyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl, isoxazolyl, isothiazolyl, triazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrazinyl, triazinyl, benzofuranyl, benzothiopheneyl, benzimidazolyl, benzooxazolyl, benzothiazolyl, benzotriazolyl, indolyl, inazolyl, quinolinyl, isoquinolinyl, naphridinyl, quinazolinyl, quinoxolinyl, phthalazinyl, pyrazolo[3,4-b]pyridinyl.

[0114] Exemplary 5-membered heteroaryl groups containing one heteroatom include, but are not limited to, pyrroleyl, furanyl, and thiophenyl. Exemplary 5-membered heteroaryl groups containing two heteroatoms include, but are not limited to, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, and isothiazolyl. Exemplary 5-membered heteroaryl groups containing three heteroatoms include, but are not limited to, triazolyl, oxadiazolyl, and thiadiazolyl. Exemplary 5-membered heteroaryl groups containing four heteroatoms include, but are not limited to, tetrazolyl. Exemplary 6-membered heteroaryl groups containing one heteroatom include, but are not limited to, pyridinyl. Exemplary 6-membered heteroaryl groups containing two heteroatoms include, but are not limited to, pyridinyl, pyrimidinyl, and pyrazinyl. Exemplary 6-membered heteroaryl groups containing three or four heteroatoms include, but are not limited to, triazinyl and tetraazinyl, respectively. Exemplary 7-membered heteroaryl groups containing one heteroatom include, but are not limited to, aziridine, oxaziridine, and thioaziridine. Exemplary 5,6-bicyclic heteroaryl groups include, but are not limited to, indolyl, isoindolyl, indazole, benzotriazolyl, benzothiophenyl, isobenzothiophenyl, benzofuranyl, benzoisofuranyl, benzoimidazolyl, benzoxazolyl, benzoisoxazolyl, benzoxadiazolyl, benzothiazolyl, benzoisothiazolyl, benzothiadiazolyl, indazinyl, and purinyl. Exemplary 6,6-bicyclic heteroaryl groups include, but are not limited to, naphthidyl, pteridyl, quinolinyl, isoquinolinyl, cenolinyl, quinoxalinyl, phthalazinyl, and quinazolinyl.

[0115] "Heteroaryl" is a subset of alkyl and heteroaryl, referring to an alkyl group that is optionally substituted with a heteroaryl group.

[0116] In the context of this invention, preferred heteroaryl groups are monocyclic or optionally bicyclic 5-10-membered heteroaryl groups containing at most two heteroatoms selected from the N, O, and / or S series. Particularly preferred are monocyclic 5- or 6-membered heteroaryl groups containing at most two heteroatoms selected from the N, O, and / or S series, such as furanyl, thiophene, thiazolyl, oxazolyl, isothiazolyl, isoxazolyl, pyrazolyl, imidazole, pyridinyl, pyrimidinyl, pyridazinyl, and pyrazinyl.

[0117] The invention will be further illustrated by the accompanying schematic drawings and experimental details. In the drawings, the following figures are shown:

[0118] Figure 1 Synthesis of self-supported IDP catalysts (Example 1)

[0119] Figure 2 Self-loaded type i Synthesis of IDP catalysts (Examples 3, 4, 6, 7, 8, 9, 10, 11, 13)

[0120] Figure 3 Synthesis of self-supported IDPi catalysts (Examples 16-26)

[0121] Figure 4 Synthesis of self-supported phosphoric acid catalysts (Example 27)

[0122] Figure 5 Synthesis of self-supported PADI catalysts (Example 28)

[0123] Figure 6 Results of the recycling experiment

[0124] Figure 7: Characterization of the catalyst in Example 4

[0125] Experimental Section

[0126] Example 1: Synthesis of a self-supported IDP catalyst

[0127] A (S,S)-IDP catalyst, 4,4'-azaalkyldiylbis(2,6-bis(perfluoronaphthyl-2-yl)dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphazene 4-oxide (50 mg, 1 equivalent), 4,4'-biphenol (21.9 mg, 2.1 equivalent), NaH (11.7 mg, 10 equivalent), and DMF (0.5 mL) were charged into a flame-drying flask equipped with a magnetic stir bar. The mixture was stirred at 25 °C for 48 h. It was then cooled to 0 °C and quenched with a 10% aqueous HCl solution. The reaction mixture was filtered, and the solid was washed with water, then with organic solvents (MeOH, EtOAc, Et2O, and pentane) and dried to give a pale yellow powder (82% yield). This solid material was then used for catalysis without further purification.

[0128] Example 2: Synthesis of self-supported IDP catalyst

[0129] A (S,S)-IDP catalyst, 4,4'-azaalkyldiylbis(2,6-bis(perfluoronaphthyl-2-yl)dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphazene 4-oxide) (50 mg, 1 equivalent), 4,4'-biphenol (116 mg, 2.1 equivalent), K₂CO₃ (246 mg, 6 equivalent), and DMSO (5 mL) were charged into a flame-drying flask equipped with a magnetic stir bar. The mixture was stirred at 40 °C for 1 h, at 85 °C for 2 h, and then at 145 °C for 2 h. It was then cooled to 0 °C and quenched with a 10% aqueous HCl solution. The reaction mixture was filtered, and the solid was washed with water, then with organic solvents (MeOH, EtOAc, Et₂O, and pentane) and dried to give a pale yellow powder (95% yield). This solid material was then used for catalysis without further purification.

[0130] Example 3: Self-loaded type i Synthesis of IDP catalysts

[0131] (S,S)- is added to a flame-drying flask equipped with a magnetic stir bar. i IDP catalyst [1,1,1-trifluoro-N-((2S)-4-((4-oxy-2,6-bis(perfluoronaphthyl-2-yl)dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphatidyl-4-yl)amino)-2,6-bis(perfluoronaphthyl-2-yl)-4,5-dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphatidyl-4-yl)methanesulfonamide-[1,1'-biphenyl]-4,4'-diol-ethane-1,2-diol-perfluoromethane (1 / 1 / 1 / 1)] (50 mg, 1 equivalent), 4,4'-biphenyl (21.3 mg, 2.1 equivalent), NaH (10.9 mg, 10 equivalent), and DMF (0.5 mL). The mixture was stirred at 25 °C for 48 h. The mixture was then cooled to 0°C and quenched with a 10% HCl aqueous solution. The reaction mixture was filtered and the solid was washed with water, then washed with organic solvents (MeOH, EtOAc, Et2O, and pentane) and dried to give a pale yellow powder (82% yield). The solid material was then used for catalysis without further purification.

[0132] Example 4a: Self-loading type i Synthesis of IDP catalysts

[0133] (S,S)- is added to a flame-dried flask equipped with a magnetic stir bar. i IDP catalyst [1,1,1-trifluoro-N-((2S)-4-((4-oxo-2,6-bis(perfluoronaphthyl-2-yl)dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphatidyl-4-yl)amino)-2,6-bis(perfluoronaphthyl-2-yl)-4,5-dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphatidyl-4-yl)methanesulfonamide-[1,1'-biphenyl]-4,4'-diol-ethane-1,2-diol-perfluoromethane (1 / 1 / 1 / 1)] (705 mg, 1 equivalent), 4,4'-biphenyl (152 mg, 2.1 equivalent), NaH (93 mg, 6 equivalent), and DMF (7 mL). The mixture was stirred at 25 °C for 48 h. The mixture was then cooled to 0°C and quenched with a 10% HCl aqueous solution. The reaction mixture was filtered, and the solid was washed with water, then with organic solvents (MeOH, EtOAc, Et2O, and pentane) and dried to give a pale yellow powder (93% yield). The solid material was then used for catalysis without further purification.

[0134] Example 4b: Characterization of the catalyst of Example 4a

[0135] The solid catalyst of Example 4a was characterized using the conventional technique for heterogeneous catalysts shown in Figure 7.

[0136] Powder XRD (A) shows that the synthesized catalyst is an amorphous material.

[0137] In the infrared spectrum (B), i The characteristic OH vibration peak (~3300 cm⁻¹) is absent in the IDP catalyst (black). -1 The heterogeneous catalyst exhibits the expected OH peak (red). At 820 cm⁻¹ -1 The peak in the fingerprint region is attributed to the CH bending of the 1,4-disubstituted group. This is present in both the heterogeneous catalyst and the bisphenol.

[0138] Thermogravimetric analysis (TGA) was performed under an argon atmosphere at a rate of 15 °C / min from 35 to 800 °C (C). A black material was obtained after the measurements. No melting of the compound was observed. A loss of 10% by weight was observed from 242 °C to 333 °C, and a loss of 29% by weight was observed from 570 °C.

[0139] Elemental analysis (E) shows the following percentages (%C 62.21, %H 2.39, %N 1.11, %S 1.46, %P 2.49, %O 9.79).

[0140] Finally, the obtained solid was characterized by TEM (D).

[0141] Example 5: Self-loaded type i Synthesis of IDP catalysts

[0142] (S,S)- is added to a flame-dried flask equipped with a magnetic stir bar. iIDP catalyst [1,1,1-trifluoro-N-((2S)-4-((4-oxy-2,6-bis(perfluoronaphthyl-2-yl)dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphatidyl-4-yl)amino)-2,6-bis(perfluoronaphthyl-2-yl)-4,5-dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphatidyl-4-yl)methanesulfonamide-[1,1'-biphenyl]-4,4'-diol-ethane-1,2-diol-perfluoromethane (1 / 1 / 1 / 1)] (49 mg, 1 equivalent), 4,4'-biphenyl (10 mg, 2.1 equivalent), K2CO3 (26 mg, 7 equivalent), and DMSO (1 mL). The mixture was stirred at 85 °C for 24 h. The mixture was then cooled to 0°C and quenched with a 10% HCl aqueous solution. The reaction mixture was filtered, and the solid was washed with water, then with organic solvents (MeOH, EtOAc, Et2O, and pentane) and dried to give a pale yellow powder (97% yield). The solid material was then used for catalysis without further purification.

[0143] Example 6: Self-loaded type i Synthesis of IDP catalysts

[0144] (S,S)- is added to a flame-dried flask equipped with a magnetic stir bar. i IDP catalyst [1,1,1-trifluoro-N-((2S)-4-((4-oxo-2,6-bis(perfluoronaphthyl-2-yl)dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphatidyl-4-yl)amino)-2,6-bis(perfluoronaphthyl-2-yl)-4,5-dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphatidyl-4-yl)methanesulfonamide-[1,1'-biphenyl]-4,4'-diol-ethane-1,2-diol-perfluoromethane (1 / 1 / 1 / 1)] (50 mg, 1%), 2,6-binaphthol (30.7 mg, 4 equivalents), NaH (7.2 mg, 10 equivalents), and DMF (0.5 mL). The mixture was stirred at 25 °C for 48 h. The mixture was then cooled to 0°C and quenched with a 10% HCl aqueous solution. The reaction mixture was filtered, and the solid was washed with water, then with organic solvents (MeOH, EtOAc, Et2O, and pentane) and dried to give a light brown powder (56% yield). The solid material was then used for catalysis without further purification.

[0145] Example 7: Self-loaded type i Synthesis of IDP catalysts

[0146] (S,S)- is added to a flame-dried flask equipped with a magnetic stir bar. iIDP catalyst [1,1,1-trifluoro-N-((2S)-4-((4-oxo-2,6-bis(perfluoronaphthyl-2-yl)dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphatidyl-4-yl)amino)-2,6-bis(perfluoronaphthyl-2-yl)-4,5-dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphatidyl-4-yl)methanesulfonamide-[1,1'-biphenyl]-4,4'-diol-ethane-1,2-diol-perfluoromethane (1 / 1 / 1 / 1)] (50 mg, 1 equivalent), [1,1'-biphenyl]-4,4'-dithiol (23.9 mg, 4 equivalent), NaH (7.2 mg, 10 equivalent) and DMF (0.5 mL). The mixture was stirred at 25°C for 48 h. It was then cooled to 0°C and quenched with a 10% HCl aqueous solution. The reaction mixture was filtered, and the solid was washed with water, then with organic solvents (MeOH, EtOAc, Et2O, and pentane) and dried to give a light brown powder (56% yield). This solid material was then used for catalysis without further purification.

[0147] Example 8: Self-loaded type i Synthesis of IDP catalysts

[0148] (S,S)- is added to a flame-dried flask equipped with a magnetic stir bar. i IDP catalyst [1,1,1-trifluoro-N-((2S)-4-((4-oxo-2,6-bis(perfluoronaphthyl-2-yl)dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphatidyl-4-yl)amino)-2,6-bis(perfluoronaphthyl-2-yl)-4,5-dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphatidyl-4-yl)methanesulfonamide-[1,1'-biphenyl]-4,4'-diol-ethane-1,2-diol-perfluoromethane (1 / 1 / 1 / 1)] (50 mg, 1 equivalent), [1,1'-biphenyl]-4,4'-dicarboxylic acid (26 mg, 4 equivalent), NaH (7.2 mg, 10 equivalent) and DMF (0.5 mL). The mixture was stirred at 25°C for 48 h. It was then cooled to 0°C and quenched with a 10% HCl aqueous solution. The reaction mixture was filtered, and the solid was washed with water, then with organic solvents (MeOH, EtOAc, Et2O, and pentane) and dried to give a white powder (31% yield). This solid material was then used for catalysis without further purification.

[0149] Example 9: Self-loaded type i Synthesis of IDP catalysts

[0150] (S,S)- is added to a flame-dried flask equipped with a magnetic stir bar.i IDP catalyst [1,1,1-trifluoro-N-((2S)-4-((4-oxo-2,6-bis(perfluoronaphthyl-2-yl)dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphatidyl-4-yl)amino)-2,6-bis(perfluoronaphthyl-2-yl)-4,5-dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphatidyl-4-yl)methanesulfonamide-[1,1'-biphenyl]-4,4'-diol-ethane-1,2-diol-perfluoromethane (1 / 1 / 1 / 1)] (50 mg, 1 equivalent), bisphenol A (24.5 mg, 4 equivalent), NaH (7.2 mg, 10 equivalent), and DMF (0.5 mL). The mixture was stirred at 25 °C for 48 h. The mixture was then cooled to 0°C and quenched with a 10% HCl aqueous solution. The reaction mixture was filtered, and the solid was washed with water, then with organic solvents (MeOH, EtOAc, Et2O, and pentane) and dried to give a white powder (51% yield). The solid material was then used for catalysis without further purification.

[0151] Example 10: Self-loading type i Synthesis of IDP catalysts

[0152] (S,S)- is added to a flame-dried flask equipped with a magnetic stir bar. i IDP catalyst [1,1,1-trifluoro-N-((2S)-4-((4-oxo-2,6-bis(perfluoronaphthyl-2-yl)dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphatidyl-4-yl)amino)-2,6-bis(perfluoronaphthyl-2-yl)-4,5-dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphatidyl-4-yl)methanesulfonamide-[1,1'-biphenyl]-4,4'-diol-ethane-1,2-diol-perfluoromethane (1 / 1 / 1 / 1)] (50 mg, 1 equivalent), 1,6-hexanediol (12.7 mg, 4 equivalent), NaH (7.2 mg, 10 equivalent), and DMF (0.5 mL). The mixture was stirred at 25 °C for 48 h. The mixture was then cooled to 0°C and quenched with a 10% HCl aqueous solution. The reaction mixture was filtered, and the solid was washed with water, then with organic solvents (MeOH, EtOAc, Et2O, and pentane) and dried to give a white powder (35% yield). The solid material was then used for catalysis without further purification.

[0153] Example 11: Self-loaded type i Synthesis of IDP catalysts

[0154] (S,S)- is added to a flame-dried flask equipped with a magnetic stir bar. iIDP catalyst [1,1,1-trifluoro-N-((2S)-4-((4-oxo-2,6-bis(perfluoronaphthyl-2-yl)dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphatidyl-4-yl)amino)-2,6-bis(perfluoronaphthyl-2-yl)-4,5-dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphatidyl-4-yl)methanesulfonamide-[1,1'-biphenyl]-4,4'-diol-ethane-1,2-diol-perfluoromethane (1 / 1 / 1 / 1)] (50 mg, 1 equivalent), benzene-1,3,5-triol (6.7 mg, 2 equivalents), NaH (7.2 mg, 10 equivalents), and DMF (0.5 mL). The mixture was stirred at 25 °C for 48 h. The mixture was then cooled to 0°C and quenched with a 10% HCl aqueous solution. The reaction mixture was filtered, and the solid was washed with water, then with organic solvents (MeOH, EtOAc, Et2O, and pentane) and dried to give a white powder (35% yield). The solid material was then used for catalysis without further purification.

[0155] Example 12: Self-loading type i Synthesis of IDP catalysts

[0156] (S,S)- is added to a flame-dried flask equipped with a magnetic stir bar. i IDP catalyst [1,1,1-trifluoro-N-((2S)-4-((4-oxo-2,6-bis(perfluoronaphthyl-2-yl)dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphatidyl-4-yl)amino)-2,6-bis(perfluoronaphthyl-2-yl)-4,5-dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphatidyl-4-yl)methanesulfonamide-[1,1'-biphenyl]-4,4'-diol-ethane-1,2-diol-perfluoromethane (1 / 1 / 1 / 1)] (50 mg, 1 equivalent), 2,6-dihydroxynaphthalene (9.3 mg, 2.1 equivalent), K₂CO₃ (19 mg, 5 equivalent), and DMSO (1 mL). The mixture was stirred at 85 °C for 24 h. The mixture was then cooled to 0°C and quenched with a 10% HCl aqueous solution. The reaction mixture was filtered, and the solid was washed with water, then with organic solvents (MeOH, EtOAc, Et2O, and pentane) and dried to give a pale yellow powder (53% yield). The solid material was then used for catalysis without further purification.

[0157] Example 13: Self-loaded type i Synthesis of IDP catalysts

[0158] (S,S)- is added to a flame-dried flask equipped with a magnetic stir bar. iIDP catalyst [1,1,1-trifluoro-N-((2S)-4-((4-oxo-2,6-bis(perfluoronaphthyl-2-yl)dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphatidyl-4-yl)amino)-2,6-bis(perfluoronaphthyl-2-yl)-4,5-dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphatidyl-4-yl)methanesulfonamide-[1,1'-biphenyl]-4,4'-diol-ethane-1,2-diol-perfluoromethane (1 / 1 / 1 / 1)] (26.7 mg, 1 equivalent), 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirodiindane (10 mg, 2 equivalents), K2CO3 (20.3 mg, 10 equivalents) and DMSO (1 mL). The mixture was stirred at 85 °C for 16 h. It was then cooled to 0 °C and quenched with a 10% HCl aqueous solution. The reaction mixture was filtered, and the solid was washed with water, then with organic solvents (MeOH, EtOAc, Et2O, and pentane) and dried to give a pale yellow powder (32% yield). The solid material was then used for catalysis without further purification.

[0159] Example 14: Self-loaded type i Synthesis of IDP catalysts

[0160] (S,S)- is added to a flame-dried flask equipped with a magnetic stir bar. i IDP catalyst [1,1,1-trifluoro-N-((2S)-4-((4-oxo-2,6-bis(perfluoronaphthyl-2-yl)dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphatidyl-4-yl)amino)-2,6-bis(perfluoronaphthyl-2-yl)-4,5-dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphatidyl-4-yl)methanesulfonamide-[1,1'-biphenyl]-4,4'-diol-ethane-1,2-diol-perfluoromethane (1 / 1 / 1 / 1)] (48.79 mg, 1 equivalent), 4,4'-biphenyl (10 mg, 2.0 equivalent), lithium hydroxide monohydrate (3.2 mg, 5 equivalent), and DMSO (1 mL). The mixture was stirred at room temperature for 24 h. It was then cooled to 0°C and quenched with a 10% HCl aqueous solution. The reaction mixture was filtered, and the solids were dissolved during washing with an organic solvent.

[0161] Example 15: Self-loading type i Synthesis of IDP catalysts

[0162] (S,S)- is added to a flame-dried flask equipped with a magnetic stir bar. iIDP catalyst [1,1,1-trifluoro-N-((2S)-4-((4-oxo-2,6-bis(perfluoronaphthyl-2-yl)dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphatidyl-4-yl)amino)-2,6-bis(perfluoronaphthyl-2-yl)-4,5-dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphatidyl-4-yl)methanesulfonamide-[1,1'-biphenyl]-4,4'-diol-ethane-1,2-diol-perfluoromethane (1 / 1 / 1 / 1)] (50 mg, 1 equivalent), 4,4'-biphenyl (20.5 mg, 4.0 equivalent), Cs₂CO₃ (89.7 mg, 10 equivalent), and DMSO (1 mL). The mixture was stirred at room temperature for 24 h. The mixture was then cooled to 0°C and quenched with a 10% HCl aqueous solution. The reaction mixture was filtered, and the solid was washed with water, then with organic solvents (MeOH, EtOAc, Et2O, and pentane) and dried to give a pale yellow powder (53% yield). The solid material was then used for catalysis without further purification.

[0163] Example 16: Synthesis of self-supported IDPi catalyst

[0164] A (S,S)-IDPi catalyst N,N'-((2S,2'S)-azaalkyldiylbis(2,6-bis(perfluoronaphthyl-2-yl)-4,5-dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphazene-4-yl-4-ylidene))bis(1,1,1-trifluoromethanesulfonamide) (50 mg, 1 equivalent), 4,4'-biphenol (18.9 mg, 4 equivalent), NaH (10.2 mg, 10 equivalent), and DMF (0.5 mL) were charged into a flame-dried flask equipped with a magnetic stir bar. The mixture was stirred at 25 °C for 48 h. It was then cooled to 0 °C and quenched with a 10% HCl aqueous solution. The reaction mixture was filtered, and the solid was washed with water, then washed with organic solvents (MeOH, EtOAc, Et2O, and pentane) and dried to give a pale yellow powder (91% yield). The solid material was then used for catalysis without further purification.

[0165] Example 17: Synthesis of self-supported IDPi catalyst

[0166] A (S,S)-IDPi catalyst, N,N'-(azanediylbis(2,6-bis(4-(tert-butyl)phenyl)-4,5-dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphazen-4-yl-4-ylidene))bis(1,3,4,5,6,7,8-heptafluoronaphthalene-2-sulfonamide) (300 mg, 1 equivalent), 4,4'-biphenol (60.8 mg, 2.1 equivalent), NaH (39.2 mg, 6 equivalent), and DMF (3 mL) were charged into a flame-dried flask equipped with a magnetic stir bar. The mixture was stirred at 25 °C for 48 h. It was then cooled to 0 °C and quenched with a 10% aqueous HCl solution. The reaction mixture was filtered, and the solid was washed with water, then washed with organic solvents (MeOH, EtOAc, Et2O, and pentane) and dried to give a pale yellow powder (86% yield). The solid material was then used for catalysis without further purification.

[0167] Example 18: Synthesis of self-supported IDPi catalyst

[0168] A flame-dried flask equipped with a magnetic stir bar was filled with (S,S)-IDPi catalyst N,N'-(azinediylbis(2,6-bis(4-(tert-butyl)phenyl)-4,5-dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphazene-4-yl-4-ylidene))bis(2,3,4,5,6-pentafluorobenzenesulfonamide)-[1,1'-biphenyl]-4,4'-diol-ethane-1,2-diol-perfluoromethane (1 / 1 / 1 / 1) (35 mg, 1 equivalent), 4,4'-biphenyl (4.4 mg, 1 equivalent), K2CO3 (16.2 mg, 5 equivalent), and DMSO (1 mL). The mixture was stirred at 145 °C for 48 h. It was then cooled to 0 °C and quenched with a 10% HCl aqueous solution. The reaction mixture was filtered, and the solid was washed with water, then with organic solvents (MeOH, EtOAc, Et2O, and pentane) and dried to give a pale yellow powder (39% yield). This solid material was then used for catalysis without further purification.

[0169] Example 19: Synthesis of self-supported IDPi catalyst

[0170] A flame-dried flask equipped with a magnetic stir bar was filled with (S,S)-IDPi catalyst N,N'-(azaalkyldiylbis(2,6-bis([1,1'-biphenyl]-3-yl)-4,5-dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphazene-4-yl-4-ylidene))bis(1,3,4,5,6,7,8-heptafluoronaphthalene-2-sulfonamide) (100 mg, 1 equivalent), 4,4'-biphenyl (19.5 mg, 2.1 equivalent), NaH (10.5 mg, 5 equivalent), and DMF (1 mL). The mixture was stirred at 25 °C for 48 h. It was then cooled to 0 °C and quenched with a 10% HCl aqueous solution. The reaction mixture was filtered, and the solid was washed with water, then with organic solvents (MeOH, EtOAc, Et2O, and pentane) and dried to give a pale yellow powder (89% yield). This solid material was then used for catalysis without further purification.

[0171] Example 20: Synthesis of a self-supported IDPi catalyst

[0172] A (S,S)-IDPi catalyst, N,N'-(azaalkyldiylbis(2,6-bis(naphthyl-2-yl)-4,5-dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphazene-4-yl-4-ylidene))bis(2,3,4,5,6-pentafluorobenzenesulfonamide) (35.2 mg, 1 equivalent), 4,4'-biphenol (4 mg, 1 equivalent), K₂CO₃ (11.8 mg, 4 equivalent), and DMSO (1 mL) were charged into a flame-dried flask equipped with a magnetic stir bar. The mixture was stirred at 145 °C for 24 h. It was then cooled to 0 °C and quenched with a 10% aqueous HCl solution. The reaction mixture was filtered, and the solid was washed with water, then washed with organic solvents (MeOH, EtOAc, Et₂O, and pentane) and dried to give a pale yellow powder (72% yield). This solid material was then used for catalysis without further purification.

[0173] Example 21: Synthesis of self-supported IDPi catalyst

[0174] A (S,S)-IDPi catalyst N,N'-(azaalkyldiylbis(2,6-di(benzofuran)-4,5-dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphazene-4-yl-4-yl))bis(2,3,4,5,6-pentafluorobenzenesulfonamide) (1 / 1 / 1 / 1) (50.5 mg, 1 equivalent), 4,4'-biphenol (5.9 mg, 1 equivalent), K₂CO₃ (21.9 mg, 5 equivalent), and DMSO (1 mL) were charged into a flame-dried flask equipped with a magnetic stir bar. The mixture was stirred at 150 °C for 48 h. It was then cooled to 0 °C and quenched with a 10% aqueous HCl solution. The reaction mixture was filtered, and the solid was washed with water, then washed with organic solvents (MeOH, EtOAc, Et₂O, and pentane) and dried to give a pale yellow powder (53% yield). The solid material was then used for catalysis without further purification.

[0175] Example 22: Synthesis of self-supported IDPi catalyst

[0176] A flame-dried flask equipped with a magnetic stir bar was filled with (S,S)-IDPi catalyst N,N'-(azinediylbis(2,6-bis(spiro[cyclopentane-1,9'-fluorene]-2'-yl)-4,5-dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphazene-4-yl-4-ylidene))bis(2,3,4,5,6-pentafluorobenzenesulfonamide) (50 mg, 1 equivalent), 4,4'-biphenol (5 mg, 1.1 equivalent), K2CO3 (13.9 mg, 4 equivalent), and DMSO (1 mL). The mixture was stirred at 145 °C for 48 h. It was then cooled to 0 °C and quenched with a 10% HCl aqueous solution. The reaction mixture was filtered, and the solid was washed with water, then washed with organic solvents (MeOH, EtOAc, Et2O, and pentane) and dried to give a pale yellow powder (69% yield). This solid material was then used for catalysis without further purification.

[0177] Example 23: Synthesis of self-supported IDPi catalyst

[0178] A flame-dried flask equipped with a magnetic stir bar was filled with (S,S)-IDPi catalyst N-(4-((2,6-bis(3-hydroxyphenyl)-4-(((trifluoromethyl)sulfonyl)imino)-4,5-dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphatidyl-4-yl)amino)-2-(3-hydroxyphenyl)-6-(4-hydroxyphenyl)-4,5-dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphatidyl-4-yl)-1,1,1-trifluoromethanesulfonamide (55 mg, 1 equivalent), octafluoronaphthalene (37 mg, 4 equivalent), NaH (13.7 mg, 10 equivalent), and DMF (13.7 mg, 10 equivalent). The mixture was stirred at 25 °C for 48 h. The mixture was then cooled to 0°C and quenched with a 10% HCl aqueous solution. The reaction mixture was filtered, and the solid was washed with water, then washed with organic solvents (MeOH, EtOAc, Et2O, and pentane) and dried to obtain a soluble material, which was then suspended in pentane to obtain a brown powder (11% yield). This solid material was then used for catalysis without further purification.

[0179] Example 24: Synthesis of self-supported IDPi catalyst

[0180] A flame-dried flask equipped with a magnetic stir bar was filled with (S,S)-IDPi catalyst N,N'-(azinediylbis(2,6-bis(3-bromophenyl)-4,5-dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphazen-4-yl-4-ylidene))bis(1,1,1-trifluoromethanesulfonamide)-[1,1'-biphenyl]-4,4'-diol-ethane-1,2-diol-perfluoromethane (1 / 1 / 1 / 1) (50 mg, 1 equivalent), 4,4'-biphenyl diboronic acid (31 mg, 4 equivalent), Pd(PPh3)4 (3.7 mg, 0.1 equivalent), K2CO3 (26.6 mg, 6 equivalent), and THF-water (5:1; 1 mL and 0.2 mL). The mixture was stirred at 80 °C for 48 h. The mixture was then cooled to 0°C and quenched with a 10% HCl aqueous solution. The reaction mixture was filtered, and the solid was washed with water, then with organic solvents (MeOH, EtOAc, Et2O, and pentane) and dried to give a light brown powder (77% yield). This solid material was then used for catalysis without further purification.

[0181] Example 25: Synthesis of a self-supported IDPi catalyst

[0182] A flame-dried flask equipped with a magnetic stir bar was filled with (S,S)-IDPi catalyst N,N'-(azaalkyldiylbis(2,6-bis(6-bromonaphthyl-2-yl)-4,5-dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphazene-4-yl-4-ylidene))bis(1,1,1-trifluoromethanesulfonamide) (50 mg, 1 equivalent), 4,4'-biphenyldiboronic acid (27.8 mg, 4 equivalent), Pd(PPh3)4 (3.3 mg, 0.1 equivalent), K2CO3 (23.5 mg, 6 equivalent), and THF-water (5:1; 0.9 mL and 0.18 mL). The mixture was stirred at 80 °C for 48 h. It was then cooled to 0 °C and quenched with a 10% HCl aqueous solution. The reaction mixture was filtered, and the solid was washed with water, then washed with organic solvents (MeOH, EtOAc, Et2O, and pentane) and dried to give a gray powder (50% yield). This solid material was then used for catalysis without further purification.

[0183] Example 26: Synthesis of self-supported IDPi catalyst

[0184] The (S,S)-IDPi catalyst N-((4S)-4-(((4S)-2,6-bis(3,5-bis(trifluoromethyl)phenyl)-9,14-bis(perfluoronaphthyl-2-yl)-4-(((trifluoromethyl)sulfonyl)imino)-4,5-dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphatidyl-4-yl)amino)-2,6-bis(3,5-bis(trifluoromethyl)phenyl)-9-(perfluoronaphthyl-2-yl)-4,5-dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphatidyl-4-yl)-1,1,1-trifluoromethanesulfonamide-methane (1 / 2) was charged into a flame-dried flask equipped with a magnetic stirrer. The mixture was prepared with 40 mg (1 equivalent), 4,4'-biphenyl (4.4 mg, 1.5 equivalent), K₂CO₃ (10.8 mg, 5 equivalent), and DMSO (1 mL). The mixture was stirred at 85 °C for 2 h, then at 150 °C for 3 h. It was then cooled to 0 °C and quenched with a 10% aqueous HCl solution. The reaction mixture was filtered, and the solid was washed with water, then with organic solvents (Et₂O and pentane) and dried to give a light brown powder (28% yield). This solid material was then used for catalysis without further purification.

[0185] Example 27: Synthesis of self-supported phosphoric acid catalyst

[0186] A flame-dried flask equipped with a magnetic stir bar was filled with (2S)-4-hydroxy-2,6-bis(perfluoronaphthyl-2-yl)dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphazene 4-oxide (50 mg, 1 equivalent), 4,4'-biphenol (21.8 mg, 2 equivalent), NaH (11.7 mg, 5 equivalent), and DMF (0.5 mL). The mixture was stirred at 25 °C for 48 h. It was then cooled to 0 °C and quenched with a 10% aqueous HCl solution. The reaction mixture was filtered, and the solid was washed with water, then washed with organic solvents (MeOH, EtOAc, Et2O, and pentane) and dried to give a pale yellow powder (63% yield). This solid material was then used for catalysis without further purification.

[0187] Example 28: Synthesis of a self-supported PADI catalyst

[0188] PADI catalyst N-((2S)-2,6-bis(perfluoronaphthyl-2-yl)-4-(((trifluoromethyl)sulfonyl)imino)-4,5-dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphazene-4-yl)-1,1,1-trifluoromethanesulfonamide (50 mg, 1 equivalent), 4,4'-biphenol (18.9 mg, 2 equivalents), NaH (10.2 mg, 5 equivalents), and DMF (0.5 mL) were charged into a flame-dried flask equipped with a magnetic stir bar. The mixture was stirred at 25 °C for 48 h. It was then cooled to 0 °C and quenched with a 10% HCl aqueous solution. The reaction mixture was filtered, and the solid was washed with water, then washed with organic solvents (MeOH, EtOAc, Et2O, and pentane) and dried to give a pale yellow powder (96% yield). The solid material was then used for catalysis without further purification.

[0189] Example 29: Cyclization of nerol / citral to isomentheneol: (Catalyst screening)

[0190]

[0191] In an oven-dried vial equipped with a magnetic stir bar, measure the catalyst, then add toluene (0.5 mL), and cool to the desired reaction temperature if necessary. Add the α,β-aldehyde (neraldehyde, 5.0 mL) in a single step. L, 0.029 mmol, 1.0 equivalent, Z:E ratio >95:5 (unless otherwise specified), and the reaction was stirred for 20 h. For homogeneous catalysts, the reaction was quenched with triethylamine (10 μL). Mesitylene was added as an internal standard, and the reaction was carried out by... 1Yields were determined by ¹H NMR spectroscopy. After solvent evaporation, the crude mixture was purified by preparative TLC (silica gel, 10:1 hexane / EtOAc, partially stained with KMnO4) to yield isomenthenol, a mixture of inseparable diastereomers. er and dr were determined by achiral and chiral GC.

[0192]

[0193] Example 30: Recyclability Experiment:

[0194]

[0195] The catalyst of Example 4 was measured in an oven-dried vial equipped with a magnetic stir bar, then PhMe (0.5 mL) was added and the mixture was cooled to -20 °C. An α,β-aldehyde (neraldehyde, 5.0 μL, 0.029 mmol, 1.0 equivalent, Z:E ratio >95:5, unless otherwise specified) was added in a single addition, and the reaction was stirred for 20 h. Trimethylbenzene was added as an internal standard. The reaction mixture was then rapidly centrifuged, and the solvent was decanted. The solid was then washed with PhMe (2 × 0.5 mL) and DCM (2 × 0.5 mL). After drying under high vacuum for 1 h, it was used for the next cycle. Analysis was performed as described above.

[0196] Example 31: Flow reaction:

[0197]

[0198] 6 g of the solid catalyst from Example 4 and 30 g of glass beads were charged into a flow reactor column. The stock solution of neraldehyde in cyclopentylmethyl ether (CPME) was incubated at 10°C at 5 mL / min. -1 The flow rate passed through the catalyst column. This experimental setup produced a 55% conversion of neraldehyde to isomentheneol, a yield of 50%, with an er:2 ratio and a dr ratio >20:1.

[0199] Example 32: Proton lactoneation:

[0200] The solid catalyst of Example 17 was used to evaluate its catalytic activity for the synthesis of (-)-Boivinianin A via a proton lactone esterification strategy.

[0201]

[0202] In an oven-dried vial equipped with a magnetic stir bar, the catalyst was measured, and then PhMe (0.25 mL) and carboxylic acid starting material (4.8 mg, 0.025 mmol, 1.0 equivalent) were added. The reaction was stirred at 30 °C for 36 h. Afterward, the reaction mixture was rapidly centrifuged, and the solvent was decanted. The solid was then washed with PhMe (2 × 0.5 mL). After drying under high vacuum for 1 h, it was used for the next cycle. Analyses were performed as described above. After solvent evaporation, the crude mixture was purified by preparative TLC (silica gel) and determined by chiral HPLC.

[0203] Example 33: Mukaiyama-Michael reaction:

[0204] The solid catalyst of Example 17 was used to evaluate its catalytic activity for the Mukaiyama-Michael reaction.

[0205]

[0206] In an oven-dried vial equipped with a magnetic stir bar, the catalyst (0.025 equivalents) was measured, followed by the addition of PhMe (0.25 mL) and SKA (2.5 equivalents). The reaction mixture was stirred at 25 °C for 25 min. Subsequently, the reaction mixture was cooled at -80 °C, and the corresponding ketone (0.05 mmol, 1 equivalent) was added dropwise. The reaction was stirred at the same temperature for 16 h. Upon completion, 1 drop of Et3N was added to quench the reaction. The crude mixture was purified by preparative TLC (silica gel) and determined by chiral HPLC.

[0207] Example 34: Cation transfer of aliphatic hydrocarbons:

[0208] The solid catalyst of Example 17 was used to evaluate its catalytic activity for cation transfer of aliphatic hydrocarbons.

[0209]

[0210] In an oven-dried vial equipped with a magnetic stir bar, the catalyst (0.05 equivalents) was measured, followed by the addition of n-hexane (0.25 M) and starting material (0.025 mmol, 1.0 equivalents). The reaction was stirred at 25 °C for 5 days. The crude mixture was purified by preparative TLC (silica gel) and determined by chiral GC.

[0211] Example 35: Diels-Alder reaction:

[0212] The solid catalyst of Example 26 was used to evaluate its catalytic activity for cation transfer of aliphatic hydrocarbons.

[0213]

[0214] In an oven-dried vial equipped with a magnetic stir bar, the catalyst (0.025 equivalents) was measured, followed by the addition of PhMe (0.25 M) and allyl-TBS (0.025 mmol, 1.0 equivalents). The reaction mixture was stirred at 25 °C for 15 min. Methyl cinnamate and cyclopentadiene were then added. After 16 h, the crude mixture was purified by preparative TLC (silica gel) and the ER and DR were determined by chiral HPLC.

Claims

1. A method for preparing a self-supported chiral catalyst polymer via non-radical polymerization, the method comprising the following steps: a) Make equation (I) (X) 1 ) n -C-(X 2 ) m The compounds and those selected from formula (I) and formula (II) (X) 1 ) n -L-(X 2 ) m The compound reacts with the compound to form a dimer of the reacting compound, which contains at least one unit -ᴑ-, and optionally... b) React the product of step a) with another compound selected from compounds of formula (I) and formula (II), thereby forming an oligomer of the reactant compound comprising at least two units -ᴑ-, and optionally... c) Repeat step b) at least once, thereby forming an oligomer containing an additional unit -ᴑ- in each step b). Where C represents a chiral catalyst, L represents a hydrocarbon linker, and X represents a hydrocarbon linker. 1 and X 2 The compounds of formulas (I) and (II) are selected to represent reaction pairs, whether identical or different, wherein the reaction pairs are selected from nucleophilic-electrophilic-reaction pairs or diene-dienophilic-reaction pairs. -ᴑ- indicates a unit in an oligomer chain formed by reactive chaperone pairs. Wherein n and m independently represent integers ≥1, preferably 1-8, more preferably 1-4, even more preferably 1-2, and wherein the number of C in the polymer chain is preferably 2-100,000.

2. A method for preparing a self-supported chiral catalyst polymer via non-radical polymerization, the method comprising the following steps: Make formula (I) (X) 1 ) n -C-(X 2 ) m The compound and formula (II) (X) 1 ) n -L-(X 2 ) m The compounds react in a solvent in the presence of a base for a sufficient time to complete the reaction between the compounds. Where C represents a chiral catalyst, L represents a hydrocarbon linker, and X represents a hydrocarbon linker. 1 and X 2 The same or different, and the choice of compounds of formula (I) and formula (II) to represent reaction pairs, wherein the reaction pairs are selected from nucleophilic-electrophilic-reaction pairs or diene-dienophile-reaction pairs.

3. The method according to claim 1 or 2, wherein formula (I) (X) 1 ) n -C-(X 2 ) m The compound and formula (II) (X) 1 ) n -L-(X 2 ) m The reaction of the compound is as shown in formula (I) (X) 1 ) n -C-(X 2 ) m The compound and formula (II) (X) 1 ) n -L-(X 2 ) m The compounds are carried out in a stoichiometric ratio of 1:1 to 1:10, preferably 1:2 to 1:

6.

4. The method for preparing a self-supported chiral catalyst polymer via non-radical polymerization according to any one of claims 1-3, wherein the nucleophilic group is selected from -OH, -SH, -NHR, -B(OR)2, -SiR3, -OSiR3, -NRSiR3, -MgT, -ZnT, -SnR3, -Li, -Na, -PR2, -CO2 - -CHZ2, -CHRZ, -CR=PR3, -C≡CH, -CR=CHR, -C(OSiR3)=CR2, -CR=C(OSiR3)(OR), -CR2=CHR-CR2-SiR3, -C≡N=O, -CR=NR=O, where T represents a halogen, preferably Cl, Br, or I, Z can be the same or different, and represents OTf, OTs, ONs, OMs, -CH=O, -CR=O, -C(OH)=O, -C(OR)=O, -NO2, -SO2R, or -CN, where R can be the same or different, and represents H, Cl-C 20 Straight-chain, branched, or cyclic aliphatic hydrocarbons, C3-C8 heterocyclic alkyl hydrocarbons, C6-C 20 Aromatic hydrocarbons or their partially hydrogenated aromatic forms, or C5-C 19 Mixed aromatic hydrocarbons.

5. The method for preparing a self-supported chiral catalyst polymer via non-radical polymerization according to any one of claims 1-4, wherein the electrophilic group is selected from H, F, Br, Cl, I, CN, NO2, -NR2, OTf, OTs, ONs, OMs, -CH=O, -CR=O, -C(OH)=O, -C(OR)=O, O=CR-O-RC=O, -C(Cl)=O, -C(Br)=O, -C(F)=O, -C(NR2)=O, -N=C=O, -N=C=S, -N=C=NR, -CR2Z, wherein R can be the same or different, and represents H, Cl-C 20 Straight-chain, branched, or cyclic aliphatic hydrocarbons, C3-C8 heterocyclic alkyl hydrocarbons, C6-C 20 Aromatic hydrocarbons or their partially hydrogenated aromatic forms, or C5-C 19 Heteroaromatic hydrocarbons, and Z indicates C2-C8 heterocyclic alkyl hydrocarbons.

6. The method for preparing a self-supported chiral catalyst polymer via non-radical polymerization according to claim 1, wherein the diene is a diene substituent -RC=CR-CR=CR2, wherein R can be the same or different, and represents H, C1-C 20 Straight-chain, branched, or cyclic aliphatic hydrocarbons, C3-C8 heterocyclic alkyl hydrocarbons, C6-C 20 Aromatic hydrocarbons or their partially hydrogenated aromatic forms, or C5-C 19 Mixed aromatic hydrocarbons.

7. The method for preparing a self-supported chiral catalyst polymer via non-radical polymerization according to any one of claims 1 or 6, wherein the dienophile is a dienophilic substituent -CR=CR2, wherein R can be the same or different, and represents H, C1-C 20 Straight-chain, branched, or cyclic aliphatic hydrocarbons, C3-C8 heterocyclic alkyl hydrocarbons, C6-C 20 Aromatic hydrocarbons or their partially hydrogenated aromatic forms, or C5-C 19 A heteroaromatic hydrocarbon, wherein at least one R has an electron-withdrawing group selected from the following: OTf, OTs, ONs, OMs, -CH=O, -CR=O, -C(OH)=O, -C(OR)=O, -NO2, -SO2R or -CN.

8. A method for preparing a self-supported chiral catalyst polymer via non-radical polymerization according to any one of the preceding claims, wherein the hydrocarbon linker L is selected from C1-C2. 20 Straight-chain, branched, or cyclic aliphatic hydrocarbons, C3-C8 heterocyclic alkyl groups, C6-C 20 Aromatic hydrocarbons or their partially aromatic hydrogenated forms, and C5-C 19 Mixed aromatic hydrocarbons.

9. A method for preparing a self-supported chiral catalyst polymer via non-radical polymerization according to any one of the preceding claims, wherein the catalyst C is a chiral phosphoramide imine compound represented by general formula (V): in: Y 1 and Y 2 O or NR can be represented independently of each other. N , W is preferably selected from hydrogen, halogens, and metal or cationic organic groups selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Mo, Ru, Rh, Pd, Ag, W, Re, Os, Ir, Pt, Au, Al, Pb, La, Sm, Eu, Yb, U, or substituted silicon-SiR I R II R III , where R I R II and R III Same or different, and each represents hydrogen, halogen, C1-C. 20 Straight-chain, branched, or cyclic aliphatic hydrocarbons, C3-C8 heterocyclic alkyl groups, C6-C 20 Aromatic hydrocarbons or their partially hydrogenated aromatic forms, or C5-C 19 heteroaromatic hydrocarbons R 1 R 2 R 3 and R 4 They may be independently identical or different from each other, and each is an aliphatic, heteroaliphatic, aromatic, or heteroaromatic hydrocarbon group, each optionally further substituted with one or more of the following: heterosubstituents, aliphatic, heteroaliphatic, aromatic, or heteroaromatic hydrocarbon groups. Where R 1 Can be used with R 2 R 3 Or R 4 Any of them forms a ring system, and R 2 R 3 Or R 4 The other two in the system can form a ring system with each other; and R N It is an electron-withdrawing group, and is the same or different for each N, and is selected from: i. -alkyl, -CO-alkyl, -(CO)-O-alkyl, sulfinylalkyl, sulfonylalkyl, -(P=O)-dialkyl, wherein the alkyl group is C1-C 20 Straight-chain, branched, or cyclic aliphatic hydrocarbons having at least one halogen substituent on an alkyl residue, preferably F and / or Cl substituents; ii. Aryl, -CO-aryl, -(CO)-O-aryl, sulfinylaryl, sulfonylaryl, -(P=O)-diaryl, wherein the aryl group is C6-C 18 Aromatic hydrocarbons, preferably having at least one halogen substituent on an aryl residue, preferably F and / or Cl substituents; iii. Heteroaryl, -CO-heteroaryl, -(CO)-O-heteroaryl, sulfinylheteroaryl, sulfonylheteroaryl, -(P=O)-di-heteroaryl, wherein the heteroaryl group is C2-C 20 Aromatic hydrocarbons, preferably having at least one halogen substituent on a heteroaryl residue, preferably F and / or Cl substituents; Or its tautomerism or ionic form.

10. A method for preparing a self-supported chiral catalyst polymer via non-radical polymerization according to any one of the preceding claims, wherein the catalyst C is a phosphoramidimino compound of general formula (V), wherein (R 1 and R 2 ) and (R 3 and R 4 Each ring system forms the same or different ring structures and is derived from a bridged, optionally dimer, aromatic structure selected from optionally substituted biphenyls, BINOL, TADDOL, VAPOL, SPINOL, 1,1'-binaphthyl, 1,1'-biphenanthrene, or a partially aromatic hydrogenated form of such an aromatic ring structure including 8H-BINOL. Each ring system is optionally substituted with one or more substituents, which are the same or different at each position, and each is selected from hydrogen, heterosubstituents, C1-C1 substituents. 20 Straight-chain, branched, or cyclic aliphatic hydrocarbons, C3-C8 heterocyclic alkyl groups, C6-C 20 Aromatic hydrocarbons or their partially hydrogenated aromatic forms, or C5-C 19 heteroaromatic hydrocarbons Among them, (R) 1 and R 2 ) and (R 3 and R 4 The ring structures formed are the same or different, and Where Y 1 Y 2 And W as defined in claim 9, Or its tautomers or ionic forms.

11. A method for preparing a self-supported chiral catalyst polymer via non-radical polymerization according to any one of the preceding claims, wherein catalyst C is a phosphoramide imine compound of general formula (VI): In formula (IV), the substituent R is the same or different at each position, and each is selected from hydrogen, heterosubstituents, C1-C... 20 Straight-chain, branched, or cyclic aliphatic hydrocarbons, C3-C8 heterocyclic alkyl groups, C6-C 20 Aromatic hydrocarbons or their partially hydrogenated aromatic forms, or C5-C 19 heteroaromatic hydrocarbons, and Y 1 Y 2 And W as defined in claim 9, or in its tautomer or ionic form.

12. A method for preparing a self-supported chiral catalyst polymer via non-radical polymerization according to any one of the preceding claims, wherein catalyst C is a phosphoramide imine compound represented by general formula (VII): The substituent R may be the same or different at each position, and each is selected from hydrogen, heterosubstituents, C1-C. 20 Straight-chain, branched, or cyclic aliphatic hydrocarbons, C3-C8 heterocyclic alkyl groups, C6-C 20 Aromatic hydrocarbons or their partially hydrogenated aromatic forms, or C5-C 19 heteroaromatic hydrocarbons Y 1 Y 2 And W as defined in claim 9, Or its tautomerism or ionic form.

13. A method for preparing a self-supported chiral catalyst polymer via non-radical polymerization according to any one of the preceding claims, wherein catalyst C is selected from: In the formula, the substituent R is the same or different at each position, and each is selected from hydrogen, heterosubstituents, C1-C... 20 Straight-chain, branched, or cyclic aliphatic hydrocarbons, C3-C8 heterocyclic alkyl groups, C6-C 20 Aromatic hydrocarbons or their partially hydrogenated aromatic forms, or C5-C 19 Heteroaromatic hydrocarbons, and W as defined in claim 9, or their tautomer or ionic forms.

14. A self-supported chiral catalyst polymer, which can be obtained by the method according to any one of claims 1-13.

15. Use of the self-supported chiral catalyst polymer according to claim 14 in organic synthesis.

16. Use as a chiral catalyst in the organic synthesis of self-supported chiral catalyst polymers according to claim 15, wherein the synthetic reaction is selected from aldol reactions, alkene aldol reactions, Mukaiyama aldol reactions, alkene Mukaiyama aldol reactions, Mukaiyama-Michael reactions, Michael addition, Mannich reactions, TMSCN addition to aldehydes and ketones to imines, esterification, etherification, pinacol rearrangement, acetalization, transfer acetalization, spiroacetalization and related reactions, cycloaddition, hydroamination, etc. Hydroalkoxylation, hydration, haloalkoxylation, haloamination, olefin activation (usually including alkene reactions and Prince reactions), Friedel-Crafts reaction, epoxide ring opening, Ritter reaction, nucleophilic substitution of alcohols, asymmetric ring opening, asymmetric reduction, transfer hydrogenation, alkyne addition, imine addition, Strecker reaction, allylation, propargylation, reduction, epoxidation, olefin metathesis, isomerization, Diels-Alder reaction, hetero-Diels-Alder reaction, acetal amination, imineonium catalysis, and enamine catalysis.

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