Polymeric diamine ligand, diamine ligand, preparation method therefor and use in catalytic synthesis of chiral alcohol

Abstract

Disclosed in the present invention are a polymeric diamine ligand, a diamine ligand, a preparation method therefor, and the use in catalytic synthesis of a chiral alcohol. Specifically provided in the present invention is a polymeric diamine compound, the polymeric diamine compound having a structural framework shown as formula I. A polymeric diamine metal chelate prepared from the polymeric diamine compound may be used as a catalyst in a transfer hydrogenation reaction to obtain chiral alcohol compounds having a plurality of substituents with a low catalyst loading and a high yield. Moreover, said reaction involves mild conditions, no alkali participation and simple operation and does not need special reactors.

Description

Polymeric diamine ligand, diamine ligand, preparation method thereof and application of the ligand in catalytic synthesis of chiral alcohol

[0001] This application claims priority to Chinese patent application 2024110790679 with a filing date of 2024 / 8 / 7. This application incorporates the entirety of the aforementioned Chinese patent application. TECHNICAL FIELD

[0002] The present application relates to a polymeric diamine ligand, a diamine ligand, a preparation method thereof and an application of the ligand in catalytic synthesis of chiral alcohol. BACKGROUND

[0003] Asymmetric transfer hydrogenation (ATH) employs formic acid or alcohol as hydrogen source, compared to direct hydrogenation, asymmetric transfer hydrogenation has become an indispensable method in the synthesis of chiral alcohol or chiral amine in synthetic organic chemistry due to its inherent safer chemical properties, easy operation and no need for special reactor characteristics (J. Am. Chem. Soc. 2019, 141, 2661.). Among them, in particular, the use of substituted 1,2-diamine or amino alcohol as chiral ligand of semi-sandwich structure η 6 Aryl ring metal catalyst (Noyori-Ikariya catalyst) has shown excellent asymmetric transfer hydrogenation enantioselectivity for carbonyl or imine in both academic and industrial fields (J. Am. Chem. Soc. 1995, 117, 7562; J. Am. Chem. Soc. 1996, 118, 2521; J. Am. Chem. Soc. 2005, 127, 7318; J. Am. Chem. Soc. 2011, 133, 14960; J. Am. Chem. Soc. 2019, 141, 16354.). Although asymmetric transfer hydrogenation has made great progress in the past three decades, compared to asymmetric hydrogenation, it still faces many limitations, such as the surprising gap in the amount of catalyst used. Asymmetric transfer hydrogenation with more than 10000 turnovers is rarely reported.

[0004] Ligand structure plays an important role in achieving high enantioselectivity. Since there is still no general solution for asymmetric transfer hydrogenation catalyst, the modification of ligand based on electronic and steric hindrance is still the key to achieve the best ee value. Our group recently reported the asymmetric reductive coupling of chiral diamines mediated by diboron, which provides the possibility for the fine-tuning of Noyori-Ikariya catalyst. Combined with the recent reports by Ogo (Organometallics 1999, 18, 5470; J. Am. Chem. Soc. 2002, 124, 597.), Fukuzumi (J. Am. Chem. Soc. 2003, 125, 4149; J. Am. Chem. Soc. 2004, 126, 3020.) and Carreira (Org. Lett. 2009, 11, 4196; Org. Lett. 2010, 12, 2893.) on the asymmetric transfer hydrogenation of functionalized ketones in aqueous solution using unfunctionalized diamine trivalent iridium catalyst, a series of chiral diamine ligand library can be quickly adopted to provide high enantioselectivity mode for this type of reductive reaction.

[0005] In order to achieve asymmetric transfer hydrogenation catalyst recycling and high conversion, chemists have developed silicon-based (Dalton Trans. 2011, 40, 2338.), polymer (RSC Adv. 2013, 3, 6747.), ionic liquid (ACS Appl. Polym. Mater. 2020, 2, 1268.) or micellar (Org. Lett. 2022, 24, 4099.) supported Noyori-Ikariya catalysts, which exhibit considerable activity and enantioselectivity and catalyst recyclability. In general, supported catalysts can achieve 3-10 times of the similar catalyst activity and enantioselectivity of normal non-supported Noyori-Ikariya catalysts. However, because the total conversion is still significantly lower than the asymmetric hydrogenation method, the supported Noyori-Ikariya catalyst has not been widely used in industry.

[0006] Developing new industrial high conversion supported asymmetric transfer hydrogenation catalysts, not only achieving catalyst recycling, but further demonstrating its efficiency through low catalyst loading, is an important research direction. The important problem is how to develop a supported asymmetric transfer hydrogenation catalyst that is superior to non-polymeric ATH catalysts. To solve this problem, the supported ATH catalyst should in principle solve the deactivation problem of Noyori-Ikariya catalyst and exhibit longer catalyst life compared to non-supported catalysts. Currently, there is still no ideal report on the supported ATH catalyst for this problem. SUMMARY

[0007] The present application provides a polymeric diamine ligand, a diamine ligand and a preparation method thereof and application of catalytic synthesis of chiral alcohol, which overcomes the defects of high catalyst dosage, low optical purity or single type of substituent in the prior art asymmetric transfer hydrogenation for synthesizing chiral compounds.

[0008] The present application solves the above technical problems through the following technical solutions.

[0009] The present application provides a polymeric diamine compound, which has a structural framework as shown in formula I:

[0010] wherein the configurations of the carbon atoms marked with "*" and "*1" are independently R configuration, S configuration or a mixture of the two;

[0011] R 1 and R 2 are each independently hydrogen or C1-C6 alkyl;

[0012] -L- is C6-C10 arylene optionally substituted with 1, 2 or 3 R 3 ; or 10 ; or

[0013] are each independently C6-C10 arylene; 10

[0014] m is independently 0, 1, 2 or 3;

[0015] R 3 , R 3a , R 3b and R 3c are each independently C1-C6 alkyl optionally substituted with 1, 2 or 3 R 3a-1 ; or

[0016] R 3a-1 is independently halogen;

[0017] n is 20 to 50.

[0018] ​In an embodiment of the application, each of said C1-C6alkyl and C1-C6alkyl of substituted C1-C6alkyl is independently methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl, or s-butyl; for example, methyl.

[0019] In an embodiment of the application, each of said C6-C10aryl and C6-C10aryl of substituted C6-C10aryl is independently phenyl. 10 10 In an embodiment of the application, each of said C6-C10aryl and C6-C10aryl of substituted C6-C10aryl is independently phenyl. 10 In an embodiment of the application, each of said C6-C10aryl and C6-C10aryl of substituted C6-C10aryl is independently phenyl.

[0020] In an embodiment of the application, said halogen is independently fluorine, chlorine, bromine, or iodine; for example, fluorine.

[0021] In an embodiment of the application, the carbon atoms marked with "*" and "*1" have the same configuration, for example, both are R configuration or both are S configuration.

[0022] In an embodiment of the application, the carbon atoms marked with "*" and "*1" represent an equimolar mixture of R and S configurations.

[0023] In an embodiment of the application, n is 20-35; for example, 23, 24, 26, 30, or 31.

[0024] In an embodiment of the application, R 1 is hydrogen.

[0025] In an embodiment of the application, R 2 is C1-C6alkyl, for example, methyl.

[0026] In an embodiment of the application, -L- is wherein x is 1, 2, or 3;

[0027] -L- is, for example,

[0028] -L- is further, for example,

[0029] In an embodiment of the application, said structural framework of formula I is any one of the following structures:

[0030] ​wherein, in the structure represented by Formula I-1, I-2, I-3, I-4, I-5 or I-6, the carbon atoms marked with "*" and "*1" are both in R configuration; or, the carbon atoms marked with "*" and "*1" are both in S configuration; or the carbon atoms marked with "*" and "*1" represent an equimolar mixture of R and S configurations.

[0031] Preferably, when the polymeric diamine compound has the structural framework represented by Formula I-1, n is 31.

[0032] Preferably, when the polymeric diamine compound has the structural framework represented by Formula I-2, n is 30.

[0033] Preferably, when the polymeric diamine compound has the structural framework represented by Formula I-3, n is 30.

[0034] Preferably, when the polymeric diamine compound has the structural framework represented by Formula I-4, n is 26.

[0035] Preferably, when the polymeric diamine compound has the structural framework represented by Formula I-5, n is 24.

[0036] Preferably, when the polymeric diamine compound has the structural framework represented by Formula I-6, n is 23.

[0037] The present application also provides a compound represented by Formula II:

[0038] wherein, the carbon atoms marked with "*2" and "*3" are independently in R configuration, S configuration or a mixture of both;

[0039] R 4 and R 5 are each independently hydrogen or C1-C6 alkyl;

[0040] R 6 and R 7 are each independently C6-C10 aryl optionally substituted with 1, 2 or 3 R 6-1 groups; 10

[0041] R 6-1 is independently halogen, C1-C6 alkyl optionally substituted with 1, 2 or 3 R 6-1-1 groups or R 6-1-1 is independently halogen;

[0042] R 6-1-2 is independently C1-C6 alkoxy, hydroxyl or C1-C6 alkyl;​

[0043] The compound represented by Formula II is not...

[0044] In one aspect of the present invention, R 4 and R 5 In this context, each of the C1-C6 alkyl groups is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, or sec-butyl; for example, methyl.

[0045] In one aspect of the present invention, R 6 and R 7 In the context, the C6-C 10 aryl and substituted C6-C 10 C6-C in aryl 10 Each of the aryl groups is independently either phenyl or naphthyl.

[0046] In one aspect of the present invention, R 6-1 In this context, each of the halogens is independently fluorine, chlorine, bromine, or iodine; for example, fluorine, chlorine, or bromine.

[0047] In one aspect of the present invention, R 6-1 In the C1-C6 alkyl group and the substituted C1-C6 alkyl group, the C1-C6 alkyl group is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl or sec-butyl; for example, methyl or tert-butyl.

[0048] In one aspect of the present invention, R 6-1-1 In this context, the halogen is independently fluorine, chlorine, bromine, or iodine; for example, fluorine.

[0049] In one aspect of the present invention, R 6-1-2 In this context, the alkoxy groups of C1-C6 are independently methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, or tert-butoxy; for example, methoxy.

[0050] In one aspect of the present invention, R 6-1-2 In this invention, each of the C1-C6 alkyl groups is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, or sec-butyl. In one embodiment of the invention, R... 6 and R 7 Each independently is a single, double, or triple R 6-1 Replacement C6-C 10 Aryl groups.

[0051] In one aspect of the present invention, R 6-1 Independently halogenated, by one, two or three Rs6-1-1 Substituted C1-C6 alkyl or Preferably, it is composed of 1, 2, or 3 Rs. 6-1-1 Substituted C1-C6 alkyl groups.

[0052] In one aspect of the present invention, R 6-1-2 Alkoxy groups are independently C1-C6.

[0053] In one embodiment of the present invention, the carbon atoms marked with "*2" and "*3" have the same configuration, for example, both are R configuration or both are S configuration.

[0054] In one embodiment of the present invention, the carbon atoms marked "*2" and "*3" indicate that the carbon atoms are an equimolar mixture of R and S configurations.

[0055] In one aspect of the present invention, R 4 and R 5 It can be hydrogen or methyl on its own.

[0056] In one aspect of the present invention, R 4 It is hydrogen.

[0057] In each embodiment of the present invention, R 5 It is a C1-C6 alkyl group, such as methyl.

[0058] In each embodiment of the present invention, R 6 and R 7 Each independently

[0059] In one aspect of the present invention, the compound represented by Formula II has any of the following structures:

[0060] This invention provides a polymeric diamine metal chelate, wherein the polymeric diamine is a polymeric diamine compound as described in any of the above embodiments, and the polymeric diamine metal chelate consists of metal M and -NR atoms on two adjacent carbon atoms in the polymeric diamine. 1 R 2 The chelate formed by chelation specifically contains one or more structural segments as shown in Formula A:

[0061] Among them, “*1”, “*”, and R 1 and R 2 The definition is as described in any of the above schemes;

[0062] Metal M is a Group VIII transition metal;

[0063] R is H2O or Cl;

[0064] said D is a cyclopentadienyl group optionally substituted with one or more R d1 substituted C6-C 10 aryl groups or a cyclopentadienyl group optionally substituted with one or more R d2 substituted C6-C

[0065] R d1 and R d2 each independently is a C1-C6 alkyl group.

[0066] In an embodiment of the present application, in D, said C6-C 10 aryl groups and said substituted C6-C 10 aryl groups, each independently is a phenyl group or a naphthyl group. 10

[0067] In an embodiment of the present application, in R d1 and R d2 , each independently is a C1-C6 alkyl group; for example, a methyl group.

[0068] In an embodiment of the present application, said R is H2O.

[0069] In an embodiment of the present application, said D is a cyclopentadienyl group optionally substituted with one or more R d2 substituted C6-C d2 aryl groups; for example, a cyclopentadienyl group substituted with one or more R d2 substituted C6-C d2 aryl groups.

[0070] In an embodiment of the present application, said metal M is ruthenium, rhodium or iridium; preferably iridium.

[0071] In an embodiment of the present application, said structural fragment of formula A is

[0072] In an embodiment of the present application, in said polymeric diamine metal chelate, the anion paired with said cationic structural fragment of formula A is denoted as (X)w, wherein X is a monovalent or divalent anion, and w is 1 or 2, said w being 2 when said X is a monovalent anion and said w being 1 when X is a divalent anion.

[0073] Preferably, when said X is a monovalent anion, said X is a halide anion; for example, Cl - .

[0074] Preferably, when said X is a divalent anion, said X is SO4 2- .

[0075] The present application provides a diamine metal chelate, said diamine metal chelate being a compound of formula B,

[0076] Among them, the carbon atoms marked with "*2" and "*3" have independently R configuration, S configuration, or a mixture of both;

[0077] R 4’ and R 5’ Each is independently hydrogen or a C1-C6 alkyl group;

[0078] R 6’ and R 7’ Each can be independently selected by 1, 2, or 3 Rs. 7-1 Replacement C6-C 10 aryl;

[0079] R 7-1 Independently halogenated, optionally by one, two, or three Rs 7-1-1 Substituted C1-C6 alkyl or

[0080] R 7-1-1 Halogens are independent of each other;

[0081] R 7-1-2 Independently, it is an alkoxy, hydroxyl, or C1-C6 alkyl group;

[0082] The definitions of R, D, X, w, and metal M are as described in any embodiment of the present invention;

[0083] The compound shown in Formula B is not...

[0084] In one aspect of the present invention, R 4’ and R 5’ In this context, each of the C1-C6 alkyl groups is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, or sec-butyl; for example, methyl.

[0085] In one aspect of the present invention, R 6’ and R 7’ In the context, the C6-C 10 aryl and substituted C6-C 10 C6-C in aryl 10 Each of the aryl groups is independently either phenyl or naphthyl.

[0086] In one aspect of the present invention, R 7-1 In this context, each of the halogens is independently fluorine, chlorine, bromine, or iodine; for example, fluorine, chlorine, or bromine.

[0087] In one aspect of the present invention, R 7-1In the C1-C6 alkyl group and the substituted C1-C6 alkyl group, the C1-C6 alkyl group is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl or sec-butyl; for example, methyl or tert-butyl.

[0088] In one aspect of the present invention, R 7-1-1 In this context, the halogen is independently fluorine, chlorine, bromine, or iodine; for example, fluorine.

[0089] In one aspect of the present invention, R 7-1-2 In this context, the alkoxy groups of C1-C6 are independently methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, or tert-butoxy; for example, methoxy.

[0090] In one aspect of the present invention, R 7-1-2 In this context, each of the C1-C6 alkyl groups is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, or sec-butyl.

[0091] In one embodiment of the present invention, the carbon atoms marked with "*2" and "*3" have the same configuration, for example, both are R configuration or both are S configuration.

[0092] In one embodiment of the present invention, the carbon atoms marked "*2" and "*3" indicate that the carbon atoms are an equimolar mixture of R and S configurations.

[0093] In one aspect of the present invention, R 6’ and R 7’ Each independently is a single, double, or triple R 6-1 Replacement C6-C 10 Aryl groups.

[0094] In one aspect of the present invention, R 7-1 Independently halogenated, by one, two or three Rs 7-1-1 Substituted C1-C6 alkyl or Preferably, it is composed of 1, 2, or 3 Rs. 7-1-1 Substituted C1-C6 alkyl groups.

[0095] In one aspect of the present invention, R 7-1-2 Alkoxy groups are independently C1-C6.

[0096] In one aspect of the present invention, R 4’ and R 5’ It can be hydrogen or methyl on its own.

[0097] In one aspect of the present invention, R 4’ It is hydrogen.

[0098] In each embodiment of the present invention, R5’ It is a C1-C6 alkyl group, such as methyl.

[0099] In one aspect of the present invention, R 6’ and R 7’ Each independently

[0100] In one embodiment of the present invention, the diamine metal chelate has any of the following structures:

[0101] This invention also provides the application of polymeric diamine metal chelates or diamine metal chelates as described above as catalysts in the asymmetric transfer hydrogenation reaction to prepare chiral alcohol compounds.

[0102] In one embodiment of the present invention, the asymmetric transfer hydrogenation reaction includes the following steps: in a solvent, in the presence of an acid and substance S, compound A1 undergoes the asymmetric transfer hydrogenation reaction as described below to prepare compound B1.

[0103] Among them, the carbon atoms marked with "*4" have independently R configuration, S configuration, or a mixture of both;

[0104] R 8 For optional use by one or more R 8-1 Replacement C6-C 10 aryl, optionally with one or more R 8-2 Substituted C1-C6 alkyl groups, optionally with one or more R 8-3 Substituted C3-C6 cycloalkyl groups, optionally with one or more R 8-4 The substituted heteroatom is selected from one, two, or three of N, O, and S, and is a 3-6 membered heterocyclic alkyl group having one, two, or three heteroatoms, or optionally is replaced by one or more R... 8- 5 The substituted heteroatoms are selected from one, two, or three of N, O, and S, and are 5-10 membered heteroaryl groups with one, two, or three heteroatoms.

[0105] R 8-1 R 8-2 R 8-3 R 8-4 and R 8-5 Each is independently halogenated, hydroxyl-containing, or optionally coated with one or more R atoms. 8-1-1 Substituted C1-C6 alkyl groups, optionally with one or more R 8-1-2 Substituted C1-C6 alkoxy groups, optionally with one or more R groups 8-1-3 Replacement C6-C 10 The aryl group may be optionally enclosed by one or more R groups.8-1-3 substituted C3-C6cycloalkyl;

[0106] R 8-1-1 and R 8-1-2 independently halogen;

[0107] R 8-1-3 independently C1-C6alkyl, C1-C6alkoxy or halogen;

[0108] R 9 is optionally substituted C1-C6alkyl or 9-1 C1-C6alkoxy;

[0109] R 9-1 independently halogen, cyano or nitro;

[0110] R 9-2 independently hydroxy or C1-C6alkoxy;

[0111] or, "R 8-1 and R 9 " or "R 8-5 and R 9 " together with the atom to which they are attached form a 3-6 membered heterocycloalkenyl optionally substituted with 1, 2 or 3 R 9a groups; said 3-6 membered heterocycloalkenyl containing, in addition to 1 or 2 heteroatom groups , 1, 2 or 3 heteroatoms selected from N, O and S;

[0112] R 9a independently C1-C6alkyl;

[0113] or, R 8 and R 9 together with the atom to which they are attached form a 3-6 membered saturated heterocyclic ring optionally substituted with 1, 2 or 3 R 9b groups; said 3-6 membered saturated heterocyclic ring containing, in addition to 1 or 2 heteroatom groups , 1, 2 or 3 heteroatoms selected from N, O and S;

[0114] R 9b independently C1-C6alkyl;

[0115] said substance S is a polymeric diamine metal chelate and / or a diamine metal chelate as described previously.

[0116] In one embodiment of the present application, said "one or more" is 1, 2 or 3.

[0117] In an embodiment of the application, R 8 In an embodiment of the application, the C6-C 10 In an embodiment of the application, the C6-C 10 In an embodiment of the application, the C6-C 10 In an embodiment of the application, the C6-C

[0118] In an embodiment of the application, R 8 In an embodiment of the application, the C1-C6alkyl and C1-C6alkyl in substituted C1-C6alkyl are each independently methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl, or s-butyl; for example,

[0119] In an embodiment of the application, R 8 In an embodiment of the application, the C3-C6cycloalkyl and C3-C6cycloalkyl in substituted C3-C6cycloalkyl are each independently cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl.

[0120] In an embodiment of the application, R 8 In an embodiment of the application, the 5-10 membered heteroaryl and 5-10 membered heteroaryl in substituted 5-10 membered heteroaryl are each independently a 5-membered heteroaryl having 1 or 2 heteroatoms selected from O or S; for example,

[0121] In an embodiment of the application, R 8-1 , R 8-2 , R 8-3 , R 8-4 , and R 8-5 In an embodiment of the application, the halogen is each independently fluorine, chlorine, bromine, or iodine.

[0122] In an embodiment of the application, R 8-1 In an embodiment of the application, the C1-C6alkyl and C1-C6alkyl in substituted C1-C6alkyl are each independently methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl, or s-butyl; for example, methyl or i-propyl.

[0123] In an embodiment of the application, R 8-2 , R 8-3 , R 8-4 , and R 8-5 In an embodiment of the application, the C1-C6alkyl and C1-C6alkyl in substituted C1-C6alkyl are each independently methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl, or s-butyl.

[0124] In an embodiment of the application, R 8-1In certain embodiments of R, the C1-C6alkyl of R and the C1-C6alkyl of substituted C1-C6alkyl is each independently methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl, or s-butyl.

[0125] In certain embodiments of the application, R 8-2 , R 8-3 , R 8-4 , and R 8-5 , the C1-C6alkyl of R and the C1-C6alkyl of substituted C1-C6alkyl is each independently methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl, or s-butyl.

[0126] In certain embodiments of the application, R 8-1 , the C6-C 10 aryl of R and the C6-C 10 aryl of substituted C6-C 10 aryl is independently phenyl or naphthyl.

[0127] In certain embodiments of the application, R 8-2 , R 8-3 , R 8-4 , and R 8-5 , the C6-C 10 aryl of R and the C6-C 10 aryl of substituted C6-C 10 aryl is independently phenyl or naphthyl.

[0128] In certain embodiments of the application, R 8-1 , R 8-2 , R 8-3 , R 8-4 , and R 8-5 , the C3-C6cycloalkyl of R and the C3-C6cycloalkyl of substituted C3-C6cycloalkyl is independently cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl.

[0129] In certain embodiments of the application, R 8-1-1 , the halogen is independently fluorine, chlorine, bromine, or iodine.

[0130] In certain embodiments of the application, R 8-1-2 , the halogen is independently fluorine, chlorine, bromine, or iodine.

[0131] In certain embodiments of the application, R 8-1-3 , the C1-C6alkyl is independently methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl, or s-butyl.

[0132] In certain embodiments of the application, R 8-1-3 In certain embodiments of the application, the C1-C6alkoxy is independently methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, or t-butoxy.

[0133] In certain embodiments of the application, R 8-1-3 In certain embodiments of the application, the halo is independently fluorine, chlorine, bromine, or iodine.

[0134] In certain embodiments of the application, R 9 In certain embodiments of the application, the C1-C6alkyl and substituted C1-C6alkyl C1-C6alkyl is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, or sec-butyl; for example, methyl.

[0135] In certain embodiments of the application, R 9-1 In certain embodiments of the application, the halo is independently fluorine, chlorine, bromine, or iodine; for example, fluorine.

[0136] In certain embodiments of the application, in R9-2, the C1-C6alkoxy is independently methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, or t-butoxy; for example, methoxy.

[0137] In certain embodiments of the application, the 3-6 membered heterocycloalkenyl is independently a 5 membered heterocycloalkenyl containing 2 heteroatom groups further comprising 1 N heteroatom; for example,

[0138] In certain embodiments of the application, in R9a, the C1-C6alkyl is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, or sec-butyl; for example, methyl.

[0139] In certain embodiments of the application, the 3-6 membered saturated heterocycle is independently a 5 membered heterocycle containing 2 heteroatom groups further comprising 1 O heteroatom; for example,

[0140] In certain embodiments of the application, R8is C1-C6alkyl, C6-C10aryl optionally substituted with 1 or more R8-1, or "5-10 membered heteroaryl with 1, 2, or 3 heteroatoms selected from N, O, and S, the number of heteroatoms being 1, 2, or 3”.

[0141] In certain embodiments of the application, R8-1is independently halo, hydroxyl, C1-C6alkoxy, C6-C10aryl, C3-C6cycloalkyl, or C1-C6alkyl optionally substituted with 1 or more R8-1-1.

[0142] In one embodiment of the present application, "R8-1and R9" together with the atom to which they are attached form a 3- to 6-membered heterocycloalkenyl group substituted with 1, 2, or 3 R9a; and the 3- to 6-membered heterocycloalkenyl group contains 1 or 2 heteroatom groups In addition, the 3- to 6-membered heterocycloalkenyl group can further contain 1, 2, or 3 heteroatoms selected from N, O, and S.

[0143] In one embodiment of the present application, "R8and R9" together with the atom to which they are attached form a 3- to 6-membered saturated heterocyclic ring substituted with 1, 2, or 3 R9b; and the 3- to 6-membered saturated heterocyclic ring contains 1 or 2 heteroatom groups In addition, the 3- to 6-membered saturated heterocyclic ring can further contain 1, 2, or 3 heteroatoms selected from N, O, and S.

[0144] In one embodiment of the present application, the substance S is the polymeric diamine metal chelate compound, and when the carbon atoms marked with "*" and "*1" are both in the R configuration, the compound B1 is

[0145] In one embodiment of the present application, the substance S is the polymeric diamine metal chelate compound, and when the carbon atoms marked with "*" and "*1" are both in the S configuration, the compound B1 is

[0146] In one embodiment of the present application, the substance S is the polymeric diamine metal chelate compound, and when the carbon atoms marked with "*" and "*1" are in an equimolar mixture of the R configuration and the S configuration, the compound B1 is In one embodiment of the present application, the substance S is the polymeric diamine metal chelate compound, and when the carbon atoms marked with "*" and "*1" are in an equimolar mixture of the R configuration and the S configuration, the compound B1 is

[0147] In one embodiment of the present application, the substance S is the diamine metal chelate compound, and when the carbon atoms marked with "*2" and "*3" are both in the R configuration, the compound B1 is

[0148] In one embodiment of the present application, the substance S is the diamine metal chelate compound, and when the carbon atoms marked with "*2" and "*3" are both in the S configuration, the compound B1 is

[0149] In one embodiment of the present application, the substance S is the above-mentioned polymeric diamine metal chelate compound, and the compound B1 is the following structure: In one embodiment of the present application, the substance S is the above-mentioned polymeric diamine metal chelate compound, and the compound B1 is the following structure:

[0150] In one embodiment of the present application, R8is

[0151] In one embodiment of the present application, R 9 is

[0152] In one embodiment of the present application, when "R 8-1 and R 9 , together with the atom to which they attach, form an optionally R 9a substituted 3-6 membered heterocycloalkenyl group, the is wherein n1and n2are each independently 0, 1, 2 or 3.

[0153] In one embodiment of the present application, when R 8 and R 9 , together with the atom to which they attach, form an optionally R 9b substituted saturated 3-6 membered heterocyclic ring, the is n3is 0, 1, 2 or 3.

[0154] In one embodiment of the present application, the compound A1 is any one of the following structures:

[0155] In one embodiment of the present application, the substance S is the above-mentioned polymeric diamine metal chelate compound or the above-mentioned diamine metal chelate compound, and the compound B1 is any one of the following structures:

[0156] In one embodiment of the present application, the acid is an organic acid, for example R x1 is a C1-C6 alkyl group; and the acid is preferably formic acid.

[0157] In some embodiments of the present application, the solvent is a mixture of an organic solvent and water; the organic solvent is preferably one or more of aromatic hydrocarbon solvents, alcohol solvents, amide solvents, ether solvents and sulfoxide solvents; further preferably alcohol solvents or ether solvents; the alcohol solvent can be methanol; the ether solvent can be 1,4-dioxane; the water can be deionized water; preferably, the volume ratio of the organic solvent to the water is (1-5):(1-2); preferably 1:1.

[0158] In some embodiments of the present application, the molar ratio of the compound A1 to the acid is 1:(3-8); preferably 1:5.

[0159] In some embodiments of the present application, the molar ratio of the compound A1 to the polymeric diamine metal chelate is 1:(0.0001-0.005); preferably 1:(0.0001-0.0010), further preferably 1:0.0005.

[0160] In some embodiments of the present application, the molar ratio of the compound A1 to the metal diamine compound is 1:(0.0005-0.01); preferably 1:(0.001-0.010). Preferably 1:0.005.

[0161] In some embodiments of the present application, the molar volume ratio of the compound A1 to the solvent is (0.1-0.6) mmol / mL; preferably 0.2 mmol / mL or 0.5 mmol / mL.

[0162] In some embodiments of the present application, the reaction temperature of the asymmetric transfer hydrogenation reaction is 40-100°C, preferably 55-70°C; for example, 60°C or 70°C.

[0163] In some embodiments of the present application, the reaction time of the asymmetric transfer hydrogenation reaction is 4-24 h, preferably 8-20 h; for example, 12 h.

[0164] In some embodiments of the present application, the asymmetric transfer hydrogenation reaction is carried out under inert gas conditions; the inert gas can be nitrogen.

[0165] In some embodiments of the present application, the asymmetric transfer hydrogenation reaction further comprises the following post-treatment steps: extraction (for example, ethyl acetate extraction three times), drying the organic phase (for example, with anhydrous sodium sulfate), filtration, concentration, silica gel column chromatography purification (for example, the eluent is a mixture of dichloromethane and methanol with a volume ratio of 80:1), concentration.

[0166] In some embodiments of the present application, the reaction raw materials of the asymmetric transfer hydrogenation reaction are the solvent, the acid, the substance S and the compound A1.

[0167] This invention provides a method for preparing compound B1, which includes the following steps: in a solvent, in the presence of an acid and the aforementioned substance S, compound A1 undergoes the asymmetric transfer hydrogenation reaction described below to prepare compound B1.

[0168] R8 and R9 are defined as described in any of the above schemes;

[0169] Preferably, the reaction conditions, the proportions of each raw material, and the operating method of the asymmetric transfer hydrogenation reaction are as described in the asymmetric transfer hydrogenation reaction of any of the foregoing schemes.

[0170] This invention provides a method for preparing a polymeric diamine compound, comprising the following steps: in a solvent, in the presence of compound E, compound C undergoes a polymeric reductive coupling reaction to prepare a polymeric diamine compound having a structural framework as shown in Formula I;

[0171] in,

[0172] The carbon atoms marked with "*5" have configurations that are independently R, S, or a mixture of both.

[0173] R 10 R 11 R 12 R 13 R 14 and R 15 Each can be independently selected by 1, 2, or 3 Rs. 10-1 Replacement C6-C 10 aryl;

[0174] R 10-1 It is an alkyl group that is independently C1-C6.

[0175] The R mentioned 1 It is hydrogen or a C1-C6 alkyl group;

[0176] The R mentioned 2 It is hydrogen;

[0177] The polymeric diamine compound and the -L- are as described in any embodiment of the present invention.

[0178] In one aspect of the present invention, R 10 R 11 R 12 R 13 R 14 and R 15 In the context, the C6-C 10 aryl and substituted C6-C10 C6-C in aryl 10 Each of the aryl groups is independently either phenyl or naphthyl; for example, phenyl.

[0179] In one aspect of the present invention, R 1 and R 10-1 In this context, the alkyl group of C1-C6 is methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, or sec-butyl; for example, methyl.

[0180] In one embodiment of the present invention, the carbon atoms marked with "*5" all have the R configuration.

[0181] In one embodiment of the present invention, the carbon atoms marked with "*5" all have the S configuration.

[0182] In one embodiment of the present invention, the carbon atoms marked "*5" indicate that the carbon atoms are an equimolar mixture of R and S configurations.

[0183] In one aspect of the present invention, when the carbon atoms marked with "*5" in compound E all have the R configuration, the carbon atoms marked with "*" and "*1" in the polymeric diamine compound also have the R configuration; when the carbon atoms marked with "*5" in compound E have the S configuration, the carbon atoms marked with "*" and "*1" in the polymeric diamine compound also have the S configuration; when the carbon atoms marked with "*5" in compound E represent an equimolar mixture of R and S configurations, the carbon atoms marked with "*" and "*1" in the polymeric diamine compound represent an equimolar mixture of R and S configurations.

[0184] In one aspect of the present invention, R 10 and R 13 It is a phenyl group.

[0185] In one aspect of the present invention, R 11 R 12 R 14 and R 15 for

[0186] In one embodiment of the present invention, compound C has any of the following structures:

[0187] In one embodiment of the present invention, compound E is...

[0188] In an embodiment of the present application, in the polymerization-type reductive coupling reaction, the solvent is an aromatic hydrocarbon solvent and / or an ether solvent; preferably an ether solvent; more preferably diethyl ether and / or tetrahydrofuran; for example, tetrahydrofuran.

[0189] In an embodiment of the present application, in the polymerization-type reductive coupling reaction, the molar ratio of the compound C to the compound E is 1:(1-1.5); preferably 1:1.

[0190] In an embodiment of the present application, in the polymerization-type reductive coupling reaction, the molar volume ratio of the compound C to the solvent is (0.2-0.5) mmol / mL; preferably 0.27 mmol / mL.

[0191] In an embodiment of the present application, the reaction temperature of the polymerization-type reductive coupling reaction is 10-45℃; preferably 25-35℃.

[0192] In an embodiment of the present application, the reaction time of the polymerization-type reductive coupling reaction is 8-48 hours; preferably 24 hours.

[0193] In an embodiment of the present application, the polymerization-type reductive coupling reaction further comprises the following post-treatment steps: adjusting the pH to 2-3 with an acid (for example, hydrochloric acid, further for example 2M dilute hydrochloric acid), washing (for example, halogenated hydrocarbon solvent washing, further for example dichloromethane washing), adjusting the pH to alkaline with a base (for example, sodium hydroxide, further for example 2M aqueous sodium hydroxide solution), mixing with an organic solvent (for example, an alkane solvent, further for example n-heptane), filtering, washing the filter cake (for example, washing with a halogenated hydrocarbon solvent, an alkane solvent and water, further for example washing with dichloromethane, an alkane solvent and water), and drying to obtain the polymerization-type diamine compound.

[0194] In an embodiment of the present application, the reaction raw material of the polymerization-type reductive coupling reaction is the compound C, the solvent and the compound D.

[0195] The present application also provides a polymerization-type diamine compound prepared by the preparation method of the polymerization-type diamine compound according to any one of the above-mentioned embodiments.

[0196] The present application also provides a preparation method of a compound as shown in formula II, which comprises the following steps: in the presence of a compound E, a compound F undergoes a reductive coupling reaction in a solvent to prepare a compound as shown in formula II.

[0197] , wherein the R 5 is hydrogen, “*2”, “*3”, the compound E, the compound II, the R 6 and the R 4The definition of the compound E is as described in any one of the schemes of the present application. In a scheme of the present application, the configuration of the carbon atom marked with "*5" in the compound E is R configuration.

[0198] In a scheme of the present application, the configuration of the carbon atom marked with "*5" in the compound E is S configuration.

[0199] In a scheme of the present application, the carbon atom marked with "*5" represents an equimolar mixture of R configuration and S configuration.

[0200] In a scheme of the present application, when the configuration of the carbon atom marked with "*5" in the compound E is R configuration, the configuration of the carbon atoms marked with "*2" and "*3" in the compound as shown in formula II is also R configuration; when the configuration of the carbon atom marked with "*5" in the compound E is S configuration, the configuration of the carbon atoms marked with "*2" and "*3" in the compound as shown in formula II is also S configuration; when the carbon atom marked with "*5" in the compound E represents an equimolar mixture of R configuration and S configuration, the carbon atoms marked with "*2" and "*3" in the compound as shown in formula II represent an equimolar mixture of R configuration and S configuration.

[0201] In a scheme of the present application, the compound F is any one of the following structures:

[0202] In a scheme of the present application, in the reductive coupling reaction, the solvent is an aromatic hydrocarbon solvent and / or an ether solvent; preferably an ether solvent; further preferably diethyl ether or tetrahydrofuran; for example, tetrahydrofuran.

[0203] In a scheme of the present application, in the reductive coupling reaction, the molar ratio of the compound F to the compound E is 1: (0.5-1.2); preferably 1:0.5.

[0204] In a scheme of the present application, in the reductive coupling reaction, the molar volume ratio of the compound F to the solvent is (0.2-0.5) mmol / mL; preferably 0.4 mmol / mL.

[0205] In a scheme of the present application, the reaction temperature of the reductive coupling reaction is 10-45°C; preferably 25-35°C.

[0206] In a scheme of the present application, the reaction time of the reductive coupling reaction is 8-48 hours; preferably 24 hours.

[0207] In some embodiments of the present application, the reductive coupling reaction further comprises the following post-treatment steps: adjusting the pH of the reaction to 2-3 with an acid (e.g., hydrochloric acid, further for example 2M dilute hydrochloric acid), washing (e.g., halogenated hydrocarbon solvent washing, further for example dichloromethane washing), adjusting the pH of the reaction to alkaline (e.g., pH 11-12) with a base (e.g., sodium hydroxide, further for example 2M aqueous sodium hydroxide solution), extracting (e.g., halogenated hydrocarbon solvent extraction, further for example dichloromethane extraction), and concentrating to obtain a compound as shown in Formula II.

[0208] The present application provides a method for preparing a polymeric diamine metal chelate as described above, which comprises the following steps: carrying out a metal chelation reaction between Ia and a polymeric diamine as described above in a solvent to prepare a polymeric diamine metal chelate, and

[0209] The Ia is

[0210] In some embodiments of the present application, the polymeric diamine metal chelate is prepared by the method as described above.

[0211] The definitions of D, X, w and metal M are as described in any embodiments of the present application.

[0212] In some embodiments of the present application, the solvent in the method for preparing a polymeric diamine metal chelate is a mixed solvent of water and an alcohol solvent, and the alcohol solvent is, for example, methanol. In the mixed solvent, the volume ratio of water to the alcohol solvent is (1-3):1, for example, 1:1 or 2:1.

[0213] In some embodiments of the present application, the molar ratio of the polymeric diamine to Ia in the method for preparing a polymeric diamine metal chelate is (1-5):1, preferably 1:1.

[0214] In some embodiments of the present application, the molar volume ratio of the polymeric diamine to the solvent in the method for preparing a polymeric diamine metal chelate is (0.1-0.6) mmol / mL, preferably 0.25 mmol / mL.

[0215] In some embodiments of the present application, the aqueous solution of Ia is mixed with the alcohol solvent of the polymeric diamine to carry out the metal chelation reaction.

[0216] Preferably, the aqueous solution of Ia is added dropwise into the alcohol solvent of the polymeric diamine to carry out the metal chelation reaction.

[0217] Preferably, the water in the aqueous solution of Ia and the alcohol solvent in the alcohol solvent of the polymeric diamine are as described above.

[0218] Preferably, the aqueous solution of Ia has a molar concentration of 0.001-0.1 M, for example 0.005 M.

[0219] Preferably, the alcohol solution of the polymeric diamine has a molar concentration of 0.001-0.1 M, for example 0.005 M.

[0220] In one embodiment of the present application, the reaction temperature in the preparation method of the polymeric diamine metal chelate is 10-45°C; preferably 25-35°C.

[0221] In one embodiment of the present application, the reaction time in the preparation method of the polymeric diamine metal chelate is 8-24 hours; preferably 12 hours.

[0222] In one embodiment of the present application, the raw materials in the reaction in the preparation method of the polymeric diamine metal chelate are the solvent, Ia and the polymeric diamine.

[0223] The present application also provides a polymeric diamine metal chelate prepared by the preparation method of the polymeric diamine metal chelate according to any one of the above-mentioned embodiments.

[0224] The present application provides a preparation method of a diamine metal chelate, which comprises the following steps: subjecting Ia to a metal chelation reaction with a diamine compound in a solvent to prepare a diamine metal chelate; the Ia is as described in any one of the embodiments of the present application; the diamine compound is a compound as shown in formula II as described in any one of the embodiments of the present application.

[0225] Preferably, in the preparation method of the diamine metal chelate, the reaction conditions, the ratio of the raw materials and the operation method in the metal chelation reaction are as described in the metal chelation reaction of any one of the previous embodiments.

[0226] In one embodiment of the present application, the raw materials in the reaction in the preparation method of the diamine metal chelate are the solvent, Ia and the diamine compound.

[0227] The present application provides an application of the polymeric diamine compound as described above in the preparation of the polymeric diamine metal chelate as described above, and in the application, the preparation method of the polymeric diamine metal chelate is as described in any one of the embodiments of the present application.

[0228] The present application provides an application of the diamine compound as described above in the preparation of the diamine metal chelate as described above, and in the application, the preparation method of the diamine metal chelate is as described in any one of the embodiments of the present application.

[0229] The present application also provides a single crystal of the compound as shown in Formula X-I, which belongs to an orthorhombic system, a P 21 21 21 space group, and has a unit cell parameter of α = β = γ = 90°;

[0230] Preferably, the single crystal of the compound as shown in Formula X-I has the parameters as shown in the table:

[0231] Unless otherwise specified, the terms used in the present application have the following meanings:

[0232] The term "alkyl" refers to a straight chain or branched alkyl group having the specified number of carbon atoms (e.g., C1-C6). Alkyl groups include, but are not limited to, methyl, ethyl, t-butyl, or n-hexyl, etc.

[0233] The term "halogen" refers to fluorine, chlorine, bromine, or iodine.

[0234] The term "aryl" refers to an aromatic ring having the specified number of ring carbon atoms (e.g., C6-C 10 , consisting only of carbon atoms, which is a fused ring or a single ring. For example, a benzene ring or a naphthalene ring.

[0235] The term "arylene" refers to an aromatic group having the specified number of ring carbon atoms (e.g., C6-C 10 , consisting only of carbon atoms, which is a fused ring or a single ring. For example, phenylene or naphthylene.

[0236] The term "alkoxy" refers to a group R X -O-, wherein R X is an alkyl group as defined above.

[0237] The term "cycloalkyl" refers to a saturated cyclic group having the specified number of ring carbon atoms (e.g., C3-C6), consisting only of carbon atoms.

[0238] The term "heterocycloalkyl" refers to a saturated cyclic group having the specified number of ring atoms (e.g., 3-6 membered), the specified number of heteroatoms (e.g., 1, 2, or 3), and the specified type of heteroatoms (1, 2, or 3 of N, O, and S).

[0239] The term "heteroaryl" refers to a cyclic aromatic group having the specified number of ring atoms (e.g., 5-10 membered), the specified number of heteroatoms (e.g., 1, 2, or 3), and the specified type of heteroatoms (1, 2, or 3 of N, O, and S). Heteroaryl groups include, but are not limited to, thienyl and furanyl.

[0240] The term "heteroalkenyl" refers to a cyclic, unsaturated, monovalent or divalent hydrocarbon radical having a specified number of ring atoms (e.g., 3-6), a specified number of heteroatoms (e.g., 1, 2, or 3), a specified heteroatom or heteroatom group species (e.g., one, two, or three of N, O, and S), having one or more (e.g., 1 or 2) carbon-carbon sp2 double bonds, which is not aromatic. Heteroalkenyl groups include, but are not limited to

[0241] The term "saturated heterocycle" refers to a saturated, cyclic radical having a specified number of ring atoms (e.g., 3-6 membered), a specified number of heteroatoms (e.g., 1, 2, or 3), a specified heteroatom species (e.g., one, two, or three of N, O, and S). Saturated heterocycles include, but are not limited to

[0242] The "-" at the end of a radical indicates that the radical is attached to other fragments in the molecule at that point.

[0243] In a structural fragment, is attached to other fragments in the molecule at that point, e.g., is phenylene.

[0244] The above preferred conditions can be combined in any way, without departing from the ordinary skill of the art, to yield preferred embodiments of the present application.

[0245] The reagents and materials used in the present application are commercially available.

[0246] The positive progress effect of the present application is that the polymeric diamine compound of the present application, the polymeric diamine metal chelate prepared therefrom as a catalyst in a transfer hydrogenation reaction can obtain a variety of substituted chiral alcohol compounds with low catalyst loading and high yield, and the reaction conditions are mild, no base is needed, the operation is simple, and no special reactor is needed. BRIEF DESCRIPTION OF DRAWINGS

[0247] Figure 1 is an X-single crystal diffraction pattern of the compound as shown in formula X-I in Example 10.

[0248] Figure 2 is a partial enlarged view of the X-single crystal diffraction pattern of the compound as shown in formula X-I in Example 10. DETAILED DESCRIPTION

[0249] The present application will be further described by way of examples, but the present application is not limited to the scope of the examples. The experimental methods in the following examples, for which specific conditions are not specified, are selected according to conventional methods and conditions, or according to the instructions of the goods.

[0250] ​​Preparation of Example 1 (I-6, PDA-6)

[0251] S1. Preparation of 4-bromo-3,5-bistrifluoromethylaniline (a)

[0252] 3,5-bistrifluoromethylaniline (0.1 mol. 1.0 eq) was dissolved in anhydrous DMF (100 mL) and cooled to -20 °C, N-bromosuccinimide (0.1 mol. 1.0 eq) was added in portions, then the reaction was allowed to warm to -15 °C and continue to react for 12 hours. After the reaction was completed, it was concentrated and diluted with ethyl acetate, then washed with saturated brine and sodium thiosulfate in turn, the organic phase was collected, dried with anhydrous sodium sulfate, concentrated after drying, and the crude product was purified by silica gel column chromatography, the eluent was a mixture of petroleum ether and ethyl acetate with a volume ratio of 100:1. After the eluent containing the product (a) was concentrated and rotary evaporated, white solid 4-bromo-3,5-bistrifluoromethylaniline (a, 10.1 g, 44%) was obtained.

[0253] a: 1 H NMR (500 MHz, CDC13): δ 7.13 (s, 2H), 4.08 (s, 2H); 13 C NMR (126 MHz, CDC13): δ 145.6, 133.1, 123.6, 121.4, 119.2, 116.6, 116.6, 116.5, 116.5, 104.3; 19 F NMR (376 MHz, CDC13): δ -62.5; FI-MS: M / z 307 [M] + ; HRMS (FI) calcd for C8H4F6NBr [M] + : 306.9426; found: 306.9429.

[0254] S2. Preparation of 2,2”,6,6”-tetrakis(trifluoromethyl)-[1,1':4',1”-terphenyl]-4,4”- diamine (b-1)

[0255] Into a Schlenk tube, 4-bromo-3,5-bistrifluoromethylaniline (25 mmol, 2.5 equiv), 1,4-benzenediboronic acid (10 mmol, 1.0 equiv), palladium acetate (1 mmol, 0.1 equiv), BI-DIME (2 mmol, 0.2 equiv) and sodium carbonate (60 mmol, 6.0 equiv) were added successively, and degassed 1,4-dioxane (80 mL), deionized water (20 mL) were added successively under nitrogen protection. The reaction system was stirred at 80 °C for 9 h, and then cooled to room temperature (25 °C). The reaction mixture was filtered with celite, and the filter residue was washed with ethyl acetate for three times. The filtrate was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated. The crude product was purified by silica gel column chromatography, and the eluent was petroleum ether and ethyl acetate (8:1, by volume). The eluent containing the product was concentrated and rotary evaporated to give white solid 2,2”,6,6”-tetrakis(trifluoromethyl)-[1,1’:4’,1”-terphenyl]-4,4”-diamine (b-1, 2.6 g, 49%).

[0256] b-1: 1 H NMR (500 MHz, CDC13): δ 7.18 (d, J = 3.0 Hz, 8H), 4.07 (s, 4H); 13 C NMR (126 MHz, CDC13): δ 145.7, 134.1, 132.2 (q, J = 29.3 Hz), 129.3, 128.8, 126.5, 124.3, 122.1, 114.6 (d, J = 5.8 Hz); 19 F NMR (376 MHz, CDC13): δ -55.1; EI-MS: M / z 532 [M] + ; HRMS (EI) calcd for C 22 H 12 F 12 N2[M] + : 532.0803; found: 532.0801.

[0257] S3. Preparation of 4,4”-dibromo-2,2”-,6,6”-tetrakis(trifluoromethyl)-1,1’:4’,1”- terphenyl (c-1)

[0258] To a solution of 2,2",6,6"-tetra(trifluoromethyl)-[1,1':4',1 "-terphenyl]-4,4"- diamine (b-1, 4.0 mmol, 1.0 equiv) in 24% aqueous hydrogen bromide solution (40 mL) was added dropwise a solution of diazonium salt generated from 2 M aqueous sodium nitrite solution (32.0 mmol, 8.0 equiv) after cooling in an ice bath. CuBr (8.0 mmol, 2.0 equiv) was dissolved in 48% aqueous hydrogen bromide solution (32 mL) and warmed to 40 °C, then the diazonium salt solution was added dropwise and the reaction was stirred for 2 h. After cooling to room temperature, the reaction was quenched with saturated sodium thiosulfate solution and extracted with ethyl acetate several times, washed with saturated brine, dried over anhydrous sodium sulfate and concentrated. The crude product was purified by silica gel column chromatography using a mixture of petroleum ether and ethyl acetate (20:1, v / v) as eluent. The product-containing fractions were concentrated and dried under vacuum to give 4,4"-dibromo-2,2",6,6"-tetra(trifluoromethyl)-1,1':4',1 "-terphenyl (c-1, 1.66 g, 63%) as a white solid.

[0259] c-1: 1 H NMR (500 MHz, CDCI3): δ 8.10 (s, 4H), 7.25 (s, 4H); 13 C NMR (126 MHz, CDCI3): δ 138.5, 133.4, 133.2, 132.9, 132.7, 132.4 (d, J = 5.7 Hz), 128.7, 123.3, 121.9, 121.1, 119.0; 19 F NMR (376 MHz, CDCI3): δ -53.5; EI-MS: M / z 660 [M] + ; HRMS (EI) calcd. for C 22 H8F 12 Br2[M] + : 657.8796; found: 657.8800.

[0260] S4. 2,2",6,6"-tetra(trifluoromethyl)-[1,1':4',1 "-terphenyl]-4,4"-diformyl (III-6)

[0261] To a solution of 4,4"-dibromo-2,2",6,6"-tetra(trifluoromethyl)-1,1':4',1"- terphenyl (c-1, 2.0 mmol, 1.0 equiv) in dry tetrahydrofuran (20 mL) was added dropwise tert-butyllithium (1.3 M, 8.0 mmol, 4.0 equiv) at -78 °C under nitrogen atmosphere. The mixture was stirred for 40 min. Then DMF (6.0 mmol, 3.0 equiv) was added dropwise at -78 °C. After the addition was completed, the mixture was allowed to warm to room temperature and stirred for another 12 h. The reaction was quenched by the addition of saturated aqueous ammonium chloride solution (20 mL) and extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and concentrated. The crude product was purified by column chromatography on silica gel using a mixture of petroleum ether and ethyl acetate (10:1, v / v) as eluent. The product-containing fractions were concentrated and dried under vacuum to give 2,2",6,6"-tetra(trifluoromethyl)-[1,1':4',1"-terphenyl]-4,4"-diformyl (III-6, 0.80 g, 72%) as a white solid.

[0262] III-6: 1 H NMR (600 MHz, Acetone-d6): δ 10.33 (s, 2H), 8.66 (s, 4H), 7.49 (s, 4H); 13 C NMR (151 MHz, Acetone-d6): δ 190.1, 144.6, 136.5, 134.1, 132.0 (q, J = 30.5 Hz), 130.0 (q, J = 5.3 Hz), 128.5, 123.1 (q, J = 274.6 Hz); 19 F NMR (376 MHz, Acetone-d6): δ -58.0; FI-MS: M / z 558 [M] + ; HRMS (FI) calcd. for C 24 H 10 F 12 O2[M] + : 558.0484; found: 558.0488.

[0263] S5. N-methyl-1-(4"-(-(methylimino)methyl)-2,2",6,6"-tetra(trifluoromethyl)-[1,1'-:4',1"-terphenyl]-4-yl)methylimine (II-6)

[0264] To a mixture of 2,2",6,6"-tetra(trifluoromethyl)-[1,1':4',1"-terphenyl]-4,4"-diformyl (III-6, 1.0 mmol, 1.0 equiv), anhydrous magnesium sulfate (4.0 mmol, 4.0 equiv) and methylamine hydrochloride (3.0 mmol, 3.0 equiv) in dichloromethane (5 mL) was added triethylamine (3.6 mmol, 3.6 equiv) dropwise at 0 °C. Then, the reaction was gradually returned to room temperature and continued to stir for 3 hours. Then, it was filtered and concentrated, the resulting solid was washed with diethyl ether, and the solution was combined and concentrated to give white solid N-methyl-1-(4"-(-(methylimino)methyl)-2,2",6,6"-tetra(trifluoromethyl)-[1,1'-:4',1"-terphenyl]-4-yl)methylimine (II-6, 0.56 g, 96%).

[0265] II-6: 1 H NMR (500 MHz, CDC13): δ 8.41 (s, 2H), 8.30 (s, 4H), 7.27 (s, 4H), 3.61 (s, 6H); 1 H NMR (500 MHz, CDC13): δ 8.41 (s, 2H), 8.30 (s, 4H), 7.27 (s, 4H), 3.61 (s, 6H); 13 C NMR (126 MHz, CDC13): δ 159.3, 141.2, 136.3, 132.0 (q, J = 30.1 Hz), 128.5, 128.2 (q, J = 5.4 Hz), 123.0 (q, J = 274.8 Hz), 48.3; 19 F NMR (376 MHz, CDC13): δ -54.6; ESI-MS: M / z 585.40 [M+H] + ; HRMS (ESI) calcd. for C 26 H 17 F 12 N2[M+H] + : 585.1195; found: 585.1203.

[0266] S6. Preparation of polymeric diamine (I-6, PDA-6)

[0267] N-methyl-1-(4”-(-(methylimino)methyl)-2,2”,6,6”-tetra(trifluoromethyl)-[1,1'-:4',1”-terphenyl]-4-yl)methylimine (II-6, 0.8 mmol, 1.0 equivalent) was dissolved in tetrahydrofuran (3 mL), and chiral bisboron (CDB, 0.8 mmol, 1.0 equivalent) was added, and the reaction was allowed to proceed at room temperature for 24 hours. Thereafter, 2M dilute hydrochloric acid was added to adjust the pH of the reaction to 2-3 and washed with dichloromethane, and 2M aqueous sodium hydroxide solution was added to adjust the system to basicity, and n-heptane (10 mL) was added and filtered, and the obtained solid was washed with dichloromethane, n-heptane, and water in sequence and dried to obtain a white solid polymeric diamine (I-6, 0.37 g, 79%).

[0268] I-6: 1 H NMR (600 MHz, Methanol-d4): δ 7.63 (s, 4H), 7.11 (s, 4H), 3.83 (s, 2H), 2.32 (s, 6H). 13 C NMR (151 MHz, Methanol-d4): δ 139.2, 130.5, 129.1, 125.1, 124.3, 121.2, 119.0, 116.8, 61.6, 29.4; 19 F NMR (376 MHz, Methanol-d4): δ -58.0; Mn: 13301; Mw: 18926; MP: 11953; D (dispersion index (PDI, Mw / Mn)): 1.42. The degree of polymerization n = 23.

[0269] Preparation of Example 2 (I-5, PDA-5)

[0270] S2. Preparation of 2,2”,6,6”-tetra(trifluoromethyl)-[1,1':3',1”-terphenyl]-4,4”-diamine (b-2)

[0271] 2,2”,6,6”-tetra(trifluoromethyl)-[1,1':3',1”-terphenyl]-4,4”-diamine (b-2, 2.4 g, 45%) was prepared according to the preparation method of Reference Example 1.

[0272] b-2: 1 H NMR (500 MHz, CDCl3): δ 7.33 (t, J = 7.8 Hz, 1H), 7.23 (d, J = 7.9 Hz, 2H), 7.16 (s, 3H), 7.11 (s, 1H), 4.05 (s, 4H); 13C NMR (126 MHz, CDC13): δ 145.7, 133.3, 132.7, 130.3, 128.5, 125.6, 124.2, 122.1, 114.6; 19 F NMR (376 MHz, CDC13): δ -57.7; EI-MS: M / z 532 [M] + ; HRMS (EI) calcd for C 22 H 12 F 12 N2[M] + : 532.0803; found: 532.0810.

[0273] S3. Preparation of 4,4"-dibromo-2,2",6,6"-tetra(trifluoromethyl)-1,1':3',1"- terphenyl (c-2)

[0274] 4,4"-dibromo-2,2",6,6"-tetra(trifluoromethyl)-1,1':3',1"-terphenyl (c-2, 1.4 g, 73%) was prepared according to the preparation method of Reference Example 1.

[0275] c-2: 1 H NMR (500 MHz, CDC13): δ 8.08 (s, 4H), 7.43 (t, J = 7.8 Hz, 1H), 7.30 (d, J = 7.8 Hz, 2H), 7.12 (s, 1H); 13 C NMR (151 MHz, CDC13): δ 138.2, 133.2 (t, J = 30.9 Hz), 132.4, 132.2, 130.7, 130.2, 126.3, 125.4-118.9 (m), 122.0; 19 F NMR (376 MHz, CDC13): δ -57.9 FI-MS: M / z 660 [M] + ; HRMS (EI) calcd for C 22 H8F 12 Br2[M] + : 657.8796; found: 657.8791.

[0276] S4. Preparation of 2,2",6,6"-tetra(trifluoromethyl)-[1,1':3',1"-terphenyl]-4,4"-diformaldehyde (III-5)

[0277] 2,2",6,6"-tetra(trifluoromethyl)-[1,1':3',1"-terphenyl]-4,4"-diformaldehyde (III-5, 0.72 g, 65%) was prepared according to the preparation method of Reference Example 1.

[0278] III-5: 1 H NMR (600 MHz, Acetone-d6): δ 10.31 (s, 2H), 8.64 (s, 4H), 7.63-7.59 (t, J = 7.6 Hz, 1H), 7.52 (d, J = 6.2 Hz, 2H), 7.37 (s, 1H); 13 C NMR (151 MHz, Acetone-d6): δ 191.9, 138.3, 134.5, 133.9 (q, J = 30.1 Hz), 132.1, 132.0, 131.9 (d, J = 7.4 Hz), 128.2, 124.8 (q, J = 274.7 Hz); 19 F NMR (376 MHz, Acetone-d6): δ -57.1; FI-MS: M / z 558 [M] + ; HRMS (FI) calcd. for C 24 H 10 F 12 O2[M] + : 558.0484; found: 558.0492.

[0279] S5. Preparation of N-methyl-1-(4"-((methylimino)methyl)-2,2",6,6"- tetra(trifluoromethyl)-[1,1'-:3',1"-terphenyl]-4-yl)methylimine (II-5)

[0280] N-methyl-1-(4"-((methylimino)methyl)-2,2",6,6"-tetra(trifluoromethyl)- [1,1'-:3',1"-terphenyl]-4-yl)methylimine (II-5, 0.67 g, 89%) was prepared according to the preparation method of Reference Example 1.

[0281] II-5: 1 H NMR (500 MHz, CDCl3): δ 1 H NMR (500 MHz, CDCl3): δ 8.39 (d, J = 1.7 Hz, 2H), 8.28 (s, 4H), 7.44 (t, J = 7.7 Hz, 1H), 7.32 (d, J = 9.4 Hz, 2H), 7.17 (s, 1H); 13 C NMR (126 MHz, CDCl3): δ 159.3, 140.9, 136.3, 132.9, 132.1 (q, J = 29.7 Hz), 130.7, 130.0, 128.3, 126.1, 122.9 (q, J = 275.2 Hz), 48.3; 19F NMR (376 MHz, CDC13): δ -57.7; ESI-MS: M / z 585.20 [M+H] + ; HRMS (ESI) calcd. for C 26 H 17 F 12 N2[M+H] + : 585.1195; found: 585.1199.

[0282] S6. Preparation of polymeric diamine (I-5, PDA-5)

[0283] Polymeric diamine (I-5, 0.46 g, 68%) was prepared according to the preparation method of Reference Example 1.

[0284] I-5: 1 H NMR (500 MHz, DMSO-d6): δ 8.10-6.51 (m, 8H), 4.56 (s, 1H), 4.18 (s, 1H), 2.29 (d, 6H). 13 C NMR (151 MHz, Trifluoroacetic acid-d): δ 138.5, 130.4, 127.3, 125.9, 125.0, 122.0, 118.9, 116.7, 61.4, 58.6, 29.2; 19 F NMR (376 MHz, DMSO-d6): δ -54.6, -54.8; Mn: 13771; Mw: 14459; MP: 11939; D: 1.05. Degree of polymerization n = 24.

[0285] Preparation of Example 3 (I-4, PDA-4)

[0286] S4. Preparation of 5,5"-bis(trifluoromethyl)-[1,1':4',1"-terphenyl]-3,3"-diformyl (III-4)

[0287] Into a Schlenk tube, 3-bromo-5-trifluoromethylbenzaldehyde (6.0 mmol, 2.0 eq), 1,4-benzenediboronic acid (3.6 mmol, 1.2 eq), Pd(dppf)Cl2(0.6 mmol, 0.1 eq), sodium acetate (27 mmol, 9.0 eq) were added successively, and degassed 1,4-dioxane (30 mL), deionized water (3 mL) were added successively under nitrogen protection. The reaction system was stirred at 80 °C for 15 h and then cooled to room temperature. The reaction mixture was filtered with celite, and the filter residue was washed with ethyl acetate for three times. The filtrate was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated. The crude product was purified by silica gel column chromatography, and the eluent was petroleum ether and ethyl acetate (6:1, by volume). The eluent containing the product was concentrated and dried to obtain white solid 5,5"-bis(trifluoromethyl)-[1,1':4',1"-terphenyl]-3,3"-diformaldehyde (III-4, 0.71 g, 56%).

[0288] III-4: 1 H NMR (500 MHz, CDC13): δ 10.17 (d, J = 1.0 Hz, 2H), 8.34 (s, 2H), 8.15 (d, J = 7.1 Hz, 4H), 7.79 (d, J = 10.1 Hz, 6H); 13 C NMR (126 MHz, CDC13): δ 190.6, 142.3, 138.7, 137.5, 130.8, 129.2, 128.1, 125.7; 19 F NMR (376 MHz, CDC13): δ -60.9; FI-MS: M / z 422 [M] + ; HRMS (FI) calcd. for C 22 H 12 O2F6 [M] + : 422.0736; found: 422.0740.

[0289] S5. Preparation of N-methyl-1-(3"-((methylimino)methyl)-5,5"-bis(trifluoromethyl)- [1,1':4',1"-terphenyl]-3-yl)methylimine (II-4)

[0290] N-methyl-1-(3"-((methylimino)methyl)-5,5"-bis(trifluoromethyl)-[1,1':4',1"-terphenyl]-3- yl)methylimine (II-4, 0.62 g, 82%) was prepared according to the preparation method of Reference Example 1.

[0291] II-4: 1H NMR (500 MHz, CDC13): δ 8.41 (d, J = 1.7 Hz, 2H), 8.18 (s, 2H), 7.94 (d, J = 22.6 Hz, 4H), 7.75 (s, 4H), 3.60 (d, J = 1.6 Hz, 6H); 13 C NMR (126 MHz, CDC13): δ 160.8, 141.7, 139.1, 137.7, 131.7, 129.3, 127.8, 125.5, 123.8, 48.3; 19 F NMR (376 MHz, CDC13): δ -62.8; ESI-MS: M / z 449.28 [M+H] + ; HRMS (ESI) calcd. for C 24 H 19 F6N2[M+H] + : 449.1447; found: 449.1449.

[0292] S6. Preparation of polymeric diamine (I-4, PDA-4)

[0293] Polymeric diamine (I-4, 0.51 g, 81%) was prepared according to the preparation method of Reference Example 1.

[0294] I-4: 1 H NMR (400 MHz, DMSO-d6): δ 8.74 - 7.16 (m, 10H), 4.83 (s, 2H), 2.62 (s, 6H); 13 C NMR (151 MHz, Trifluoroacetic acid-d): δ 141.3, 138.1, 130.7, 130.7, 130.5, 128.1, 125.0, 124.3, 123.2, 121.4, 63.8, 32.3; 19 F NMR (376 MHz, Methanol-d4): δ -60.7; Mn: 11779; Mw: 12019; MP: 11018; D: 1.02. The degree of polymerization n = 26.

[0295] Preparation of Example 4 (I-3, PDA-3)

[0296] S4. Preparation of 5-(trifluoromethyl)isophthalaldehyde (III-3)

[0297] To a solution of 1,3-dibromo-5-(trifluoromethyl)benzene (10 mmol, 1.0 eq) in dry diethyl ether (20 mL) was added tert-butyllithium (1.3 M, 40 mmol, 4.0 eq) dropwise over 20 min at -78 °C with stirring. The mixture was stirred for 40 min at -78 °C. Then DMF (30 mmol, 3.0 eq) was added dropwise at -78 °C. After the addition was completed, the mixture was allowed to warm to room temperature and stirred for 12 h. The reaction was quenched by the addition of saturated aqueous ammonium chloride solution (20 mL). The mixture was extracted with ethyl acetate (3 x 20 mL). The combined organic layers were dried over anhydrous sodium sulfate and concentrated. The residue was purified by column chromatography on silica gel using petroleum ether / ethyl acetate (8:1, v / v) as eluent. The product-containing fractions were concentrated and dried under vacuum to give 5-(trifluoromethyl)isatine (III-3, 1.01 g, 50%) as a white solid.

[0298] III-3: 1 H NMR (500 MHz, CDC13): δ 10.17 (s, 2H), 8.57 (t, J = 1.6 Hz, 1H), 8.40 (dd, J = 1.5, 0.7 Hz, 2H); 13 C NMR (126 MHz, CDC13): δ 189.5, 137.6, 133.3, 132.9, 131.0 (q, J = 3.6 Hz), 122.9 (q, J = 273.1 Hz); 19 F NMR (376 MHz, CDC13): δ -63.1; FI-MS: M / z 202 [M] + ; HRMS (FI) calcd. for C9H502F3 [M + H] + : 202.0236; found: 202.0237.

[0299] S5. Preparation of N-methyl-1-(3-((methylimino)methyl)-5- (trifluoromethyl)phenyl)methanimine (II-3)

[0300] N-methyl-1-(3-((methylimino)methyl)-5-(trifluoromethyl)phenyl)methanimine (II-3, 0.81 g, 89%) was prepared according to the procedure described in Reference Example 1.

[0301] II-3: 1 H NMR (500 MHz, CDC13): δ 8.34 (q, J = 1.7 Hz, 2H), 8.15 (s, 1H), 8.04 (s, 2H), 3.56 (d, J = 1.6 Hz, 6H); 13C NMR (126 MHz, CDC13): δ 160.3, 137.5, 131.6 (t, J = 33.0 Hz), 130.6, 126.9, 126.0 (q, J = 3.7 Hz), 124.8, 122.6, 48.2; 19 F NMR (376 MHz, CDC13): δ -62.9; ESI-MS: M / z 229.30 [M+H] + ; HRMS (ESI) calcd for C 11 H 12 F3N2[M+H] + : 229.0947; found: 229.0950.

[0302] S6. Preparation of polymeric diamine (I-3, PDA-3)

[0303] Polymeric diamine (I-3, 0.64 g, 78%) was prepared according to the preparation method of Reference Example 1.

[0304] I-3: 1 H NMR (600 MHz, Trifluoroacetic acid-d): δ 8.95 - 7.70 (m, 3H), 6.29 - 5.41 (m, 2H), 3.43 - 2.11 (m, 6H); 13 C NMR (151 MHz, Trifluoroacetic acid-d): δ 133.3, 128.8, 127.2, 125.3, 118.9, 116.8, 60.1, 29.0, 28.7; 19 F NMR (376 MHz, Methanol-d4): δ -63.5; Mn: 6984; Mw: 13391; MP: 6139; D: 1.91. Degree of polymerization n = 30.

[0305] Example 5 (I-2, PDA-2) Preparation

[0306] S5. Preparation of 1,1'-(1,3-phenylene)bis(N-methylmethanimine) (II-2)

[0307] 1,1'-(1,3-phenylene)bis(N-methylmethanimine) (II-2, 2.82 g, 88%) was prepared according to the preparation method of Reference Example 1.

[0308] II-2: 1H NMR (500 MHz, CDC13): δ 8.22 (d, J = 1.7 Hz, 2H), 7.92 (s, 1H), 7.72 (dd, J = 7.7, 1.7 Hz, 2H), 7.38 (td, J = 7.6, 3.5 Hz, 1H), 3.46 (d, J = 1.7 Hz, 6H); 13 C NMR (126 MHz, CDC13): δ 161.9, 136.7, 129.5, 128.9, 127.9, 48.2; ESI-MS: M / z 161.35 [M+H] + ; HRMS (ESI) calcd. for C 10 H 13 N2[M+H] + : 161.1073; found: 161.1074.

[0309] S6. Preparation of polymeric diamine (I-2, PDA-2)

[0310] Polymeric diamine (I-2, 2.28 g, 87%) was prepared according to the preparation method of Reference Example 1.

[0311] I-2: 1 H NMR (600 MHz, DMSO-d6): δ 7.33-6.10 (m, 4H), 3.16 (s, 2H), 1.95 (s, 6H); 13 C NMR (151 MHz, DMSO-d6): δ 141.1, 126.4, 126.2, 71.1, 34.4; Mn: 4958; Mw: 5242; MP: 4243; D: 1.06, n = 30.

[0312] Preparation of Example 6 (I-1, PDA-1)

[0313] S5. Preparation of 1,1'-(1,4-phenylene)bis(N-methylmethanimine) (II-1)

[0314] 1,1'-(1,4-phenylene)bis(N-methylmethanimine) (II-1, 2.75 g, 86%) was prepared according to the preparation method of Reference Example 1.

[0315] II-1: 1 H NMR (500 MHz, CDC13): δ 8.17 (d, J = 1.7 Hz, 2H), 7.64 (s, 4H), 3.42 (d, J = 1.9 Hz, 6H); 13C NMR (126 MHz, CDC13): δ 162.0, 138.0, 128.1, 48.4; ESI-MS: M / z 161.35 [M+H] + ; HRMS (ESI) calcd for C 10 H 13 N2[M+H] + : 161.1073; found: 161.1073.

[0316] Example 6 Preparation of polymeric diamine (I-1, PDA-1)

[0317] Polymeric diamine (I-1, 2.41 g, 92%) was prepared according to the preparation method of Reference Example 1.

[0318] I-1: 1 H NMR (600 MHz, Trifluoroacetic acid-d): δ 8.46-7.45 (m, 2H), 5.79-5.21 (m, 1H), 3.42-2.21 (m, 3H). 13 C NMR (151 MHz, Trifluoroacetic acid-d): δ 133.4, 128.3, 127.9, 61.2, 29.1, 28.7; Mn: 5080; Mw: 6640; MP: 4732; 1.31, n = 31.

[0319] Example 7 Preparation of iridium polymeric diamine catalyst (P-6, Ir-PDA-6)

[0320] Under nitrogen protection, 2 mL of [Cp*Ir(H20)3](SO4) aqueous solution (0.005 M, 1.0 mmol, 1.0 equivalent) was added dropwise into 2 mL of polymeric diamine methanol solution (I-6, 0.005 M, 1.0 mmol, 1.0 equivalent). (The feeding amount was calculated according to the number average molecular weight Mn characterized by GPC (for example, in this example, the feeding amount of iridium and polymeric monomer 1 : n, n was the degree of polymerization). The reaction system was stirred at room temperature for 12 hours, and then the mixture was filtered under nitrogen atmosphere, and the filtrate was concentrated to obtain yellow solid iridium polymeric diamine catalyst (P-6, 82 mg, 59%)

[0321] Example 8 Preparation of iridium polymeric diamine catalyst (P-5, Ir-PDA-5)

[0322] Under nitrogen protection, 2 mL of [Cp*Ir(H2O)3](SO4) aqueous solution (0.005 M, 1.0 mmol, 1.0 equivalent) was added dropwise into 2 mL of polymeric diamine methanol solution (I-5, 0.005 M, 1.0 mmol, 1.0 equivalent). (The amount of raw material was calculated according to the number average molecular weight Mn characterized by GPC (for example, in this example, the amount of raw material was calculated according to the ratio of iridium to polymeric monomer 1 : n, where n is the degree of polymerization). The reaction system was stirred at room temperature for 12 hours, and then the mixture was filtered under nitrogen atmosphere, and the filtrate was concentrated to obtain a yellow solid of iridium polymeric diamine catalyst (P-5, 92 mg, 67%)

[0323] Example 9 Preparation of (1R,2R)-1,2-bis(3,5-bis(trifluoromethyl)phenyl)-N 1 , N 2 Preparation of (1R,2R)-1,2-bis(3,5-bis(trifluoromethyl)phenyl)-N

[0324] S1. Preparation of 1-(3,5-bis(trifluoromethyl)phenyl)-N-methylmethanimine (IM-10)

[0325] To a mixture of 3,5-bis(trifluoromethyl)benzaldehyde (III-1, 10 mmol, 1.0 equivalent), anhydrous magnesium sulfate (20 mmol, 2.0 equivalents) and methylamine hydrochloride (15 mmol, 1.5 equivalents) in dichloromethane (15 mL) was added triethylamine (18 mmol, 1.8 equivalents) slowly dropwise at 0 °C. Then, the reaction system was gradually returned to room temperature and continued to stir for 3 hours. Then, it was filtered and concentrated, and the obtained solid was washed with ether, and the solution was combined and concentrated to obtain 1-(3,5-bis(trifluoromethyl)phenyl)-N-methylmethanimine (IM-10, 2.14 g, 84%) as a colorless oily liquid.

[0326] II-1: 1 H NMR (500 MHz, CDCl3): δ 8.37 (s, 1H), 8.17 (s, 2H), 7.91 (s, 1H), 3.59 (s, 3H), 1.66 (s, 1H); 13 C NMR (126 MHz, CDCl3): δ 159.2, 138.1, 132.1 (d, J = 33.7 Hz), 127.7, 123.7 (d, J = 3.7 Hz), 122.0, 110.0, 48.2; 19 F NMR (376 MHz, CDCl3): δ -60.6; ESI-MS: M / z 256.00 [M+H] + ; HRMS (ESI) calcd. for C 10 H8F6N [M+H] +: 256.0555; found: 256.0555.

[0327] S2. (1R,2R)-1,2-Bis(3,5-bis(trifluoromethyl)phenyl)-N 1 , N 2 Preparation of 1,2-bis(3,5-bis(trifluoromethyl)phenyl)-N

[0328] 1-(3,5-bis(trifluoromethyl)phenyl)-N-methylmethanimine (II-1, 8 mmol, 1.0 eq) was dissolved in tetrahydrofuran (20 mL), and chiral bisboron (CDB, 4 mmol, 0.5 eq) was added, and the reaction was carried out at room temperature for 24 hours. Then 2M dilute hydrochloric acid was added to adjust the reaction pH to 2-3 and washed with dichloromethane, and 2M aqueous sodium hydroxide solution was added to adjust the reaction pH to 11-12 and extracted with dichloromethane, and the obtained solution was combined and concentrated to obtain white solid (1R,2R)-1,2-bis(3,5-bis(trifluoromethyl)phenyl)-N 1 , N 2 1,2-bis(3,5-bis(trifluoromethyl)phenyl)-N

[0329] The enantiomeric excess value (ee) of L-10 was determined by chiral high pressure liquid phase, and the ee value was 99%; high pressure liquid phase conditions: chiral S-Chiral B column, 25°C, flow rate: 0.49 mL / min, n-hexane / isopropyl alcohol / diethylamine: 99 / 1 / 0.005, 16.42 min (R, R), 18.38 min (S, S); 1 H NMR (500 MHz, CDCl3): δ 7.67 (s, 2H), 7.33 (s, 4H), 3.61 (s, 2H), 2.31 (s, 6H), 2.01 (s, 2H); 13 C NMR (126 MHz, CDCl3): δ 143.5, 131.8 (q, J = 33.3 Hz), 127.9, 123.2 (d, J = 272.8 Hz), 121.6, 71.1, 34.7; 19 F NMR (376 MHz, CDCl3): δ -58.9; ESI-MS: M / z 513.25 [M+H] + ; HRMS (ESI) calcd for C 20 H 17 F 12 N2[M+H] + : 513.1195; found: 513.1197.

[0330] Example 10

[0331] Preparation of compound X-10

[0332] Under nitrogen atmosphere, 4 mL of [Cp*Ir(H20)3](SO4) aqueous solution (0.1 M, 1.0 mmol, 1.0 equiv) was added dropwise into 2 mL of methanolic solution of (1R,2R)-1,2-bis(3,5-bis(trifluoromethyl)phenyl)-N 1 , N 2 -dimethylethane-1,2-diamine (L-10, 0.2 M, 1.0 mmol, 1.0 equiv). The reaction system was stirred at room temperature for 12 h, then the mixture was filtered under nitrogen atmosphere and the filtrate was concentrated to give yellow solid iridium catalyst (X-10, 0.33 g, 86%)

[0333] X-10: 1 H NMR (500 MHz, Methanol-d4): δ 8.88 (s, 1H), 7.85 (d, J = 4.9 Hz, 4H), 7.37 (s, 1H), 4.84 (d, J = 12.0 Hz, 1H), 4.41 (d, J = 12.0 Hz, 1H), 2.96 (s, 3H), 2.75 (s, 3H), 1.78 (s, 15H); 13 C NMR (126 MHz, Methanol-d4): δ 137.7, 136.8, 131.8, 123.9, 122.6, 122.6, 121.7, 87.6, 73.61, 71.1, 42.3, 38.1, 7.9; 19 F NMR (376 MHz, Methanol-d4): δ -66.2; MALDI: M / z 839.2 [M-HSO4-H2O] + ; HR-MALDI calcd. for C 30 H 30 IrN2F 12 [M-HSO4-H2O] + : 839.1841; found: 839.1842.

[0334] Preparation of single crystal of compound as shown in Formula X-I

[0335] The yellow solid iridium catalyst (X-10, 0.2 mmol) was dissolved in dichloromethane (5 mL) and saturated aqueous sodium chloride solution (5 mL) under nitrogen protection, stirred for 1 hour, and then the organic phase was collected, dried over anhydrous sodium sulfate and concentrated. Single crystal was cultivated by volatilization method: 5 mg of compound X-1 was weighed in a 10 mL test tube, dissolved in 1 mL of dichloromethane, and then 2 mL of n-hexane was added. The test tube was placed in a conical flask containing n-hexane, the conical flask was sealed and placed at room temperature for crystallization.

[0336] Detection method X-I Ray single crystal diffraction

[0337] It was detected that the crystal system of the compound represented by formula X-I belongs to the orthorhombic system, the P 21 21 21 space group, and the cell parameters are α= β= γ= 90°; the single crystal parameters thereof are shown in Table 1; the X-ray single crystal diffraction thereof is shown in Figure 1; and a partial enlarged view of the X-single crystal diffraction pattern of the compound represented by formula X-I is shown in Figure 2.

[0338] Table 1 Single crystal parameters and test conditions of the compound represented by formula X-I

[0339] The characterization results of the obtained X-ray single crystal diffraction indicate that the configuration of compound X-1 can be determined; and thus the configurations of X-10 and L-10 are deduced as

[0340] Example 11

[0341] The iridium diamin catalyst (X-10) prepared in Example 10 was used to prepare a chiral alcohol compound D-1a by transition metal iridium catalyzed asymmetric transfer hydrogenation reaction of ketone and formic acid (the reaction route is shown below).

[0342] The reaction procedure was as follows: 2-oxo-2-(o-tolyl)acetic acid (C-1a, 0.5 mmol, 1.0 equiv) and formic acid (2.5 mmol, 5.0 equiv) were added to a Schlenk tube containing an iridium diamine catalyst (X-10, 0.0025 mmol, 0.5 mol%) in a mixture of methanol (1.25 mL) and deionized water (1.25 mL) under nitrogen atmosphere. The reaction mixture was stirred at 70 °C for 12 h. After cooling to room temperature, saturated brine was added to the reaction mixture, and the mixture was extracted with ethyl acetate three times. The organic phase was combined, dried over anhydrous sodium sulfate, filtered, and concentrated. The crude product was purified by silica gel column chromatography eluting with a mixture of dichloromethane and methanol (80:1, v / v). The eluent containing the product (D-1a) was concentrated and dried to give (R)-2-hydroxy-2-(o-tolyl)acetic acid (D-1a) as a white solid (78 mg, 94% yield).

[0343] The enantiomeric excess value (ee) was determined by chiral high pressure liquid chromatography, and the ee value was 99%; high pressure liquid chromatography conditions: Chiral OJ-H column, flow rate: 1.0 mL / min, n-hexane / isopropyl alcohol: 90 / 10, 14.50 min (R), 20.33 min (S); [a] D 25 = -118.4 [c = 0.75, EtOH]; 1 H NMR (500 MHz, CDCl3): δ 7.34-7.14 (m, 4H), 5.42 (s, 1H), 2.41 (s, 3H); 13 C NMR (126 MHz, CDCl3): δ 177.8, 136.5, 135.9, 130.9, 128.8, 126.7, 126.4, 70.0, 19.3; ESI-MS: M / z 165.20 [M-H] - ; HRMS (ESI) calcd for C9H9Na2O3 [M+2Na-H] + : 211.0342; found: 211.0347.

[0344] Example 12

[0345] The compound polymeric diamine (I-6, PDA-6) prepared in Example 1 was used as a chiral ligand, and the iridium polymeric diamine catalyst (P-6, Ir-PDA-6) prepared in Example 7 was used to prepare the chiral alcohol compound D-1a by the transition metal iridium catalyzed asymmetric transfer hydrogenation reaction of a ketone and formic acid (the reaction route is shown below).

[0346] The reaction procedure was as follows: 2-oxo-2-(o-tolyl)acetic acid (C-1a, 2 mmol, 1.0 equiv) and formic acid (10 mmol, 5.0 equiv) were added to a Schlenk tube containing an iridium polymeric diamine catalyst (P-6, 0.001 mmol, 0.05 mol%) in a mixture of methanol (5 mL) and deionized water (5 mL) under nitrogen atmosphere. The reaction system was stirred at 60 °C for 12 h and then cooled to room temperature. Saturated brine was added to the reaction system, and the mixture was extracted with ethyl acetate three times. The organic phase was combined and dried over anhydrous sodium sulfate, filtered, and concentrated. The crude product was purified by silica gel column chromatography with dichloromethane and methanol (80:1, v / v) as eluent. The eluent containing the product (D-1a) was concentrated and dried to give (R)-2-hydroxy-2-(o-tolyl)acetic acid (D-1a) as a white solid (0.29 g, 88% yield).

[0347] The enantiomeric excess value (ee) was determined by chiral high pressure liquid chromatography, and the ee value was 95%; high pressure liquid chromatography conditions: Chiral OJ-H column, flow rate: 1.0 mL / min, n-hexane / isopropyl alcohol: 90 / 10, 14.50 min (R), 20.33 min (S); the configuration of the product was determined to be the configuration of D-1a by testing the optical rotation. 1 H NMR (500 MHz, CDC13): δ 7.34-7.14 (m, 4H), 5.42 (s, 1H), 2.41 (s, 3H); 13 C NMR (126 MHz, CDC13): δ 177.8, 136.5, 135.9, 130.9, 128.8, 126.7, 126.4, 70.0, 19.3; ESI-MS: M / z 165.20 [M-H] - ; HRMS (ESI) calcd for C9H9Na203 [M+2Na-H] + : 211.0342; found: 211.0347.

[0348] Example 13

[0349] The compound polymeric diamine (I-6, PDA-6) prepared in Example 1 was used as a chiral ligand, and the iridium polymeric diamine catalyst (P-6, Ir-PDA-6) prepared in Example 7 was used to prepare the chiral alcohol compound D-1b by transition metal iridium catalyzed asymmetric transfer hydrogenation of a ketone and formic acid according to the preparation method of Example 7 (the reaction route is shown below).

[0350] The reaction procedure was as follows: 2-(2-methoxyphenyl)-2-oxoacetic acid (C-1b, 2 mmol, 1.0 equiv) and formic acid (10 mmol, 5.0 equiv) were added to a Schlenk tube containing an iridium polymeric diamine catalyst (P-6, 0.001 mmol, 0.05 mol%) in a mixture of methanol (5 mL) and deionized water (5 mL) under nitrogen atmosphere. The reaction system was stirred at 60 °C for 12 h and then cooled to room temperature. Saturated brine was added to the reaction system, and the mixture was extracted with ethyl acetate three times. The organic phase was combined, dried over anhydrous sodium sulfate, filtered, and concentrated. The crude product was purified by silica gel column chromatography with dichloromethane and methanol (80:1, v / v) as eluent. The eluent containing the product (D-1b) was concentrated and dried to give (R)-2-hydroxy-2-(2-methoxyphenyl)acetic acid (D-1b) as a white solid (0.33 g, 90% yield).

[0351] The enantiomeric excess value (ee) was determined by chiral high pressure liquid chromatography, and the ee value was 96%; high pressure liquid chromatography conditions: chiral OD-3 column, flow rate: 1.0 mL / min, n-hexane / isopropyl alcohol: 90 / 10, 14.58 min (R), 18.43 min (S); by testing the optical rotation, it was determined that the configuration of the product was the configuration of D-1b, 1 H NMR (500 MHz, CDCl3): δ 7.32 (d, J = 7.2 Hz, 2H), 6.98 (d, J = 7.5 Hz, 1H), 6.92 (d, J = 7.7 Hz, 1H), 5.35 (s, 1H), 3.84 (s, 3H); 13 C NMR (126 MHz, CDCl3): δ 177.1, 156.7, 130.2, 129.2, 126.1, 121.2, 111.2, 69.9, 55.7; ESI-MS: M / z 205.00 [M+Na] + HRMS (ESI) calcd for C9H9Na2O4 [M+2Na-H] + : 227.0291; found: 227.0295.

[0352] Example 14

[0353] The compound polymeric diamine (I-6, PDA-6) prepared in Example 1 was used as a chiral ligand, and the iridium polymeric diamine catalyst (P-6, Ir-PDA-6) prepared in Example 7 was used to prepare the chiral alcohol compound D-1c by transition metal iridium catalyzed asymmetric transfer hydrogenation of ketone and formic acid according to the preparation method of Example 7 (the reaction route is shown below).

[0354] The reaction procedure was as follows: 2-oxo-2-(2-(trifluoromethyl)phenyl)acetic acid (C-1a, 2 mmol, 1.0 equiv) and formic acid (10 mmol, 5.0 equiv) were added to a Schlenk tube containing an iridium polymerized diamine catalyst (P-6, 0.001 mmol, 0.05 mol%) in a mixture of methanol (5 mL) and deionized water (5 mL) under nitrogen protection, and the nitrogen was replaced three times again. The reaction system was stirred at 60 °C for 12 h and then cooled to room temperature. Saturated brine was added to the reaction system, and the mixture was extracted with ethyl acetate three times. The organic phase was combined and dried over anhydrous sodium sulfate, filtered and concentrated. The crude product was purified by silica gel column chromatography, and the eluent was a mixture of dichloromethane and methanol (80:1, by volume). After the eluent containing the product (D-1c) was concentrated and dried, white solid (R)-2-hydroxy-2-(2-(trifluoromethyl)phenyl)acetic acid (D-1c) was obtained, with a yield of 0.40 g and a yield of 92%.

[0355] The enantiomeric excess value (ee) was determined by chiral high-pressure liquid chromatography, and the ee value was 96%; high-pressure liquid chromatography conditions: chiral OD-3 column, flow rate: 0.8 mL / min, n-hexane / isopropyl alcohol: 97 / 3, 14.66 min (S), 15.82 min (R); by testing the optical rotation, it was determined that the configuration of the product was the configuration of D-1c. 1 H NMR (500 MHz, Acetone-d6): δ 7.78-7.73 (m, 4H), 7.70 (t, J = 7.6 Hz, 2H), 7.56 (t, J = 7.6 Hz, 2H), 5.54 (s, 2H); 13 C NMR (126 MHz, Acetone-d6): δ 172.7, 138.7, 132.5, 129.1, 128.5, 127.7 (q, J = 30.2 Hz), 125.6 (q, J = 5.7 Hz), 123.6, 68.6; 19 F NMR (376 MHz, Acetone-d6): δ -56.8; ESI-MS: M / z 242.90 [M+Na] + ; HRMS (ESI) calcd for C9H7F3NaO3 [M+Na] + : 243.0239; found: 243.0245.

[0356] Example 15

[0357] The compound polymeric diamine (I-6, PDA-6) prepared in Example 1 was used as a chiral ligand, and the iridium polymeric diamine catalyst (P-6, Ir-PDA-6) prepared in Example 7 was used to prepare the chiral alcohol compound D-1d by the transition metal iridium catalyzed asymmetric transfer hydrogenation reaction of ketone and formic acid (the reaction route is shown below).

[0358] The reaction procedure was as follows: 2-oxo-2-phenylacetic acid (C-1d, 2 mmol, 1.0 equivalent) and formic acid (10 mmol, 5.0 equivalent) were added to a Schlenk tube containing the iridium polymeric diamine catalyst (P-6, 0.001 mmol, 0.05 mol%) in a mixture of methanol (5 mL) and deionized water (5 mL) under nitrogen protection, and the nitrogen was replaced three times again. After the reaction system was stirred at 60°C for 12 hours, it was cooled to room temperature. Saturated brine was added to the reaction system, and the mixture was extracted with ethyl acetate three times. The organic phase was dried with anhydrous sodium sulfate, filtered and concentrated. The crude product was purified by silica gel column chromatography, and the eluent was a mixture of dichloromethane and methanol (volume ratio 80:1). After the eluent containing the product (D-1d) was concentrated and rotary evaporated, white solid (R)-2-hydroxy-2-phenylacetic acid (D-1d) was obtained, with a yield of 0.27 g and a yield of 90%.

[0359] The enantiomeric excess value (ee) was determined by chiral high pressure liquid chromatography, and the ee value was 92%; the high pressure liquid chromatography conditions: chiral OD-3 column, flow rate: 1.0 mL / min, n-hexane / isopropyl alcohol: 90 / 10, 7.57 min (S), 13.56 min (R); by testing the optical rotation, it was determined that the configuration of the product was the configuration of D-1d. 1 H NMR (500 MHz, Methanol-d4): δ 7.46 (d, J = 7.0 Hz, 2H), 7.38-7.27 (m, 3H), 5.13 (s, 1H); 13 C NMR (126 MHz, Methanol-d4): δ 174.7, 139.5, 128.0, 127.8, 126.5, 72.7; ESI-MS: M / z 151.15 [M-H] - ; HRMS (ESI) calcd for C8H7Na2O3 [M+2Na-H] + : 197.0185; found: 197.0188.

[0360] Example 16

[0361] The compound polymeric diamine (I-6, PDA-6) prepared in Example 1 was used as a chiral ligand, and the iridium polymeric diamine catalyst (P-6, Ir-PDA-6) prepared in Example 7 was used to prepare the chiral alcohol compound D-1e by the transition metal iridium catalyzed asymmetric transfer hydrogenation reaction of ketone and formic acid (the reaction route is shown below).

[0362] The reaction procedure was as follows: 2,2,2-trifluoro-1-(2-methoxyphenyl)ethan-1-one (C-1a, 2 mmol, 1.0 equivalent) and formic acid (10 mmol, 5.0 equivalent) were added to a Schlenk tube containing the iridium polymeric diamine catalyst (P-6, 0.001 mmol, 0.05 mol%) in a mixture of methanol (5 mL) and deionized water (5 mL) under nitrogen protection, and the nitrogen was replaced three times again. After the reaction system was stirred at 60 °C for 12 h, it was cooled to room temperature. Saturated brine was added to the reaction system, and the mixture was extracted with ethyl acetate three times. The organic phase was combined and dried over anhydrous sodium sulfate, filtered and concentrated. The crude product was purified by silica gel column chromatography, and the eluent was a mixture of dichloromethane and methanol (80:1, by volume). After the eluent containing the product (D-1e) was concentrated and rotary evaporated, white solid (R)-2,2,2-trifluoro-1-(2-methoxyphenyl)ethan-1-ol (D-1e) was obtained in a yield of 0.40 g, 97%.

[0363] The enantiomeric excess value (ee) was determined by chiral high-pressure liquid chromatography, and the ee value was 94%; the high-pressure liquid chromatography conditions: chiral IA-3 column, flow rate: 0.8 mL / min, n-hexane / isopropyl alcohol: 95 / 5, 11.74 min (R), 12.81 min (S); by testing the optical rotation, it was determined that the configuration of the product was the configuration of D-1e. 1 H NMR (500 MHz, CDCl3): δ 7.42-7.35 (m, 2H), 7.02 (t, J = 7.5 Hz, 1H), 6.95 (d, J = 7.3 Hz, 1H), 5.29 (p, J = 7.3 Hz, 1H), 3.87 (s, 3H), 3.80 (d, J = 7.7 Hz, 1H); 13 C NMR (126 MHz, CDCl3): δ 157.5, 130.5, 129.2, 128.0, 126.2-121.8 (m), 121.0, 111.3, 69.7 (q, J = 32.6 Hz), 55.7; 19 F NMR (376 MHz, CDCl3): δ -78.6; EI-MS: M / z 206 [M] + ; HRMS (EI) calcd for C9H9F3O2 [M] +: 206.0549; found: 206.0545.

[0364] Example 17

[0365] The compound polymeric diamine (I-6, PDA-6) prepared in Example 1 was used as a chiral ligand, and the iridium polymeric diamine catalyst (P-6, Ir-PDA-6) prepared in Example 7 was used to prepare the chiral alcohol compound D-1f by the transition metal iridium catalyzed asymmetric transfer hydrogenation reaction of ketone and formic acid (the reaction route is shown below).

[0366] The reaction procedure was as follows: 1,4-dimethylindole-2,3-dione (C-1a, 2 mmol, 1.0 equivalent) and formic acid (10 mmol, 5.0 equivalent) were added to a Schlenk tube containing the iridium polymeric diamine catalyst (P-6, 0.001 mmol, 0.05 mol%) in a mixture of methanol (5 mL) and deionized water (5 mL) under nitrogen protection, and nitrogen was replaced three times again. After the reaction system was stirred at 60 °C for 12 hours, it was cooled to room temperature. Saturated brine was added to the reaction system, and the mixture was extracted with ethyl acetate three times. The organic phase was combined and dried over anhydrous sodium sulfate, filtered and concentrated. The crude product was purified by silica gel column chromatography, and the eluent was a mixture of dichloromethane and methanol (volume ratio 80:1). After the eluent containing the product (D-1f) was concentrated and rotary evaporated, white solid (R)-3-hydroxy-1,4-dimethylindole-2-one (D-1f) was obtained, with a yield of 0.34 g and a yield of 96%.

[0367] The enantiomeric excess value (ee) was determined by chiral high pressure liquid chromatography, and the ee value was 91%; high pressure liquid chromatography conditions: chiral OD-3 column, flow rate: 0.8 mL / min, n-hexane / isopropyl alcohol: 92 / 8, 15.60 min (R), 17.32 min (S); by testing the optical rotation, it was determined that the configuration of the product was the configuration of D-1f. 1 H NMR (600 MHz, CDCl3): δ 7.23 (t, J = 7.8 Hz, 1H), 6.90 (d, J = 7.8 Hz, 1H), 6.65 (d, J = 7.7 Hz, 1H), 5.06 (s, 1H), 3.18 (s, 3H), 3.07 (s, 1H), 2.43 (s, 3H); 13 C NMR (151 MHz, CDCl3): δ 176.5, 144.0, 136.8, 129.8, 124.9, 124.6, 105.9, 69.7, 26.3, 17.9; ESI-MS: M / z 200.15 [M+Na] + ; HRMS (ESI) calcd. for C10 H 11 NO2Na[M+Na] + :200.0682;found:200.0682.

[0368] Example 18

[0369] The compound polymeric diamine (I-6, PDA-6) prepared in Example 1 was used as a chiral ligand, and the iridium polymeric diamine catalyst (P-6, Ir-PDA-6) prepared in Example 7 was used to prepare the chiral alcohol compound D-1g by transition metal iridium catalyzed asymmetric transfer hydrogenation of ketone and formic acid (the reaction route is shown below).

[0370] The reaction procedure was as follows: 1-methylindole-2,3-dione (C-1a, 2 mmol, 1.0 equivalent) and formic acid (10 mmol, 5.0 equivalent) were added to a Schlenk tube containing the iridium polymeric diamine catalyst (P-6, 0.001 mmol, 0.05 mol%) in a mixture of methanol (5 mL) and deionized water (5 mL) under nitrogen protection, and nitrogen was exchanged three more times. After the reaction system was stirred at 60°C for 12 hours, it was cooled to room temperature. Saturated brine was added to the reaction system, and the mixture was extracted with ethyl acetate three times. The organic phase was dried with anhydrous sodium sulfate, filtered, and concentrated. The crude product was purified by silica gel column chromatography, and the eluent was a mixture of dichloromethane and methanol (80:1 by volume). After the eluent containing the product (D-1g) was concentrated and rotary evaporated, white solid (R)-3-hydroxy-1-methylindole-2-one (D-1g) was obtained, with a yield of 0.30 g and a yield of 91%.

[0371] The enantiomeric excess value (ee) was determined by chiral high-pressure liquid chromatography, and the ee value was 86%; high-pressure liquid chromatography conditions: chiral AD-3 column, flow rate: 1.0 mL / min, n-hexane / isopropyl alcohol: 92 / 8, 14.56 min (R), 16.73 min (S); by testing the optical rotation, it was determined that the configuration of the product was the configuration of D-1g. 1 H NMR (500 MHz, DMSO-d6): δ 7.35-7.25 (m, 2H), 7.02 (t, J = 7.5 Hz, 1H), 6.94 (d, J = 7.8 Hz, 1H), 6.22 (s, 1H), 4.88 (s, 1H), 3.06 (s, 3H); 13 C NMR (126 MHz, DMSO-d6): δ 176.5, 144.1, 129.5, 129.0, 124.8, 122.6, 108.8, 69.2, 26.2; ESI-MS: M / z 186.00 [M+Na] +HRMS (ESI) calcd for C9H9NO2Na [M+Na] 186.0525; found 186.0527. + :186.0525;found:186.0527.

[0372] Example 19

[0373] The compound polymeric diamine (I-5, PDA-5) prepared in Example 2 was used as a chiral ligand, and the iridium polymeric diamine catalyst (P-5, Ir-PDA-5) prepared in Example 8 was used to prepare the chiral alcohol compound D-1d by the transition metal iridium catalyzed asymmetric transfer hydrogenation reaction of ketone and formic acid (the reaction route is shown below).

[0374] The reaction procedure was as follows: 2-oxo-2-phenylacetic acid (C-1d, 2 mmol, 1.0 equivalent) and formic acid (10 mmol, 5.0 equivalent) were added to a Schlenk tube containing the iridium polymeric diamine catalyst (P-6, 0.001 mmol, 0.05 mol%) in a mixture of methanol (5 mL) and deionized water (5 mL) under nitrogen protection, and the nitrogen was replaced three times again. The reaction system was stirred at 60°C for 12 hours and then cooled to room temperature. Saturated brine was added to the reaction system, and the mixture was extracted with ethyl acetate three times. The organic phase was dried with anhydrous sodium sulfate, filtered and concentrated. The crude product was purified by silica gel column chromatography, and the eluent was a mixture of dichloromethane and methanol (volume ratio 80:1). After the eluent containing the product (D-1d) was concentrated and rotary evaporated, white solid (R)-2-hydroxy-2-phenylacetic acid (D-1d) was obtained, with a yield of 0.26 g, a yield of 86%, and an enantiomeric excess value (ee) of 90% determined by chiral high pressure liquid chromatography, under the same high pressure liquid chromatography conditions as in Example 15.

[0375] Example 20

[0376] The compound polymeric diamine (I-6, PDA-6) prepared in Example 1 was used as a chiral ligand, and the iridium polymeric diamine catalyst (P-6, Ir-PDA-6) prepared in Example 7 was used to prepare the chiral alcohol compound D-1d by the transition metal iridium catalyzed asymmetric transfer hydrogenation reaction of ketone and formic acid (the reaction route is shown below).

[0377] The reaction procedure was as follows: 2-oxo-2-phenylacetic acid (C-1d, 2 mmol, 1.0 equiv) and formic acid (10 mmol, 5.0 equiv) were added to a Schlenk tube containing an iridium polymeric diamine catalyst (P-6, 0.001 mmol, 0.05 mol%) in a mixture of 1,4-dioxane (5 mL) and deionized water (5 mL) under nitrogen. The reaction system was stirred at 60 °C for 12 h and then cooled to room temperature. Saturated brine was added to the reaction system, and the mixture was extracted with ethyl acetate three times. The organic phase was combined, dried over anhydrous sodium sulfate, filtered, and concentrated. The crude product was purified by silica gel column chromatography using a mixture of dichloromethane and methanol (80:1, by volume) as the eluent. The product (D-1d) was obtained as a white solid after the eluent containing the product was concentrated and dried in vacuo. The yield was 0.16 g, and the yield was 53%.

[0378] The enantiomeric excess value (ee) was determined by chiral high-pressure liquid chromatography, and the ee value was 78%; the high-pressure liquid chromatography conditions were the same as those in Example 15.

[0379] Example 21

[0380] The compound polymeric diamine (I-6, PDA-6) prepared in Example 1 was used as a chiral ligand, and the iridium polymeric diamine catalyst (P-6, Ir-PDA-6) prepared in Example 7 was used to prepare the chiral alcohol compound D-1h by transition metal iridium-catalyzed asymmetric transfer hydrogenation of a catalyst cycle involving a ketone and formic acid.

[0381] The reaction procedure is as follows: 4,4-dimethyl-2,3-dioxopentyl boronate (C-1h, 10 mmol, 1.0 equiv) and formic acid (50 mmol, 5.0 equiv) were added to a Schlenk tube containing an iridium polymer-supported diamine catalyst (P-6, 0.005 mmol, 0.05 mol%) in a mixture of methanol (10 mL) and deionized water (10 mL) under nitrogen atmosphere. The reaction system was stirred at 60 °C for 4 to 12 h and then cooled to room temperature. After each reaction, the solvent was removed by vacuum pump and the system was washed with diethyl ether (20 mL) for 5 times. The organic phase was combined, filtered and concentrated. The crude product was purified by silica gel column chromatography using a mixture of petroleum ether and ethyl acetate (3:1, v / v) as eluent. The product-containing eluent was concentrated and dried under vacuum to give the white solid D-pantoic acid lactone from one cycle. The catalyst solid in the Schlenk tube was dried and the same amount of substrate, solvent and formic acid were added under nitrogen atmosphere. The above work-up procedure was repeated and the conversion, isolated yield and ee value were determined. Finally, the products were combined to give white solid D-pantoic acid lactone (D-1h, 7.3 g, 94% isolated yield, 92% ee). After one recrystallization (diethyl ether and n-hexane as solvent), white crystalline solid D-pantoic acid lactone (D-1h, 6.9 g, 89% isolated yield, >99% ee) was obtained. The configuration of the product was determined to be D-1h by testing the optical rotation.

[0382] The experimental results are shown in Table 2:

[0383] Table 2

[0384] Example 22

[0385] The racemic polymeric diamine (I-6, PDA-6) was prepared according to the preparation method of Example 1 using racemic bis-boron CBD. Using this racemic polymeric diamine as ligand, the racemic alcohol compound was prepared by the transition metal iridium catalyzed asymmetric transfer hydrogenation reaction of ketone and formic acid according to the preparation method of Reference Example 7 and the reaction conditions of Example 11. In this example, the racemic polymeric diamine was mainly used to prepare the racemic alcohol compound in the examples, which was used as a control to determine the enantiomeric excess value (ee) of the chiral sample. The yield was similar to that of the chiral product in the above examples.

[0386] Examples 23-35

[0387] According to the preparation methods of Reference Examples 10 and 11, different diamine ligands were used as ligands to prepare corresponding iridium diamine catalysts to prepare chiral alcohol compounds D-1a with optical activity.

[0388] The reaction results are shown in Table 3:

[0389] Table 3

[0390] This result fully shows that the chiral alcohol compound can be efficiently prepared by applying the precisely controllable ligand of the present application to the asymmetric transfer hydrogenation reaction.

Claims

1. A polymeric diamine compound characterized in that, The polymeric diamine compound has a structural framework as shown in Formula I: wherein the configuration of the carbon atoms marked with "*" and "*1" is independently R configuration, S configuration or a mixture of the two; R 1 and R 2 each independently is hydrogen or Ci-C6alkyl; -L- indicates that one, two, or three R's can be selected. 3 Replacement C6-C 10 aryl or Each independently is C6-C 10 Alpha-aryl; m is independently 0, 1, 2 or 3; R 3 , R 3a , R 3b , and R 3c are each independently C1-C6alkyl optionally substituted with 1, 2, or 3 R 3a-1 ; R 3a-1 independently halogen; n is 20 to 50.

2. The polymeric diamine compound according to claim 1, wherein which satisfies one or more of the following conditions; (1) each of the C1-C6 alkyl groups in each of the C1-C6 alkyl groups and substituted C1-C6 alkyl groups is independently methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl or s-butyl; (2) Each of the C6-C 10 aryl and substituted C6-C 10 C6-C in arylene 10 The arylene group is phenylene, for example (3) the halogen is independently fluorine, chlorine, bromine or iodine; (4) the configuration of the carbon atoms marked with "*" and "*1" is the same, for example, both are R configuration or both are S configuration; or the carbon atoms marked with "*" and "*1" represent an equimolar mixture of the carbon atoms in R configuration and S configuration; (5) n is 20-35; for example, 23, 24, 26, 30 or 31; (6) R 1 is hydrogen; (7) R 2 Ci-C6-alkyl, for example methyl; (8) -L- is wherein x is 1, 2 or 3; -L- For example, -L- For example, Preferably, in the polymeric diamine compound, the structural framework as shown in Formula I is any one of the following structures: wherein, in the structure as shown in formula I-1, I-2, I-3, I-4, I-5 or I-6, the configuration of the carbon atoms marked with "*" and "*1" is both R configuration; or the configuration of the carbon atoms marked with "*" and "*1" is both S configuration; or the carbon atoms marked with "*" and "*1" represent an equimolar mixture of the carbon atoms in R configuration and S configuration; Preferably, when the polymeric diamine compound has a structural framework as shown in formula I-1, n is 31; Preferably, when the polymeric diamine compound has a structural framework as shown in formula I-2, n is 30; Preferably, when the polymeric diamine compound has a structural framework as shown in formula I-3, n is 30; Preferably, when the polymeric diamine compound has a structural framework as shown in formula I-4, n is 26; Preferably, when the polymeric diamine compound has a structural framework as shown in formula I-5, n is 24; Preferably, when the polymeric diamine compound has a structural framework as shown in formula I-6, n is 23.

3. A compound as shown in Formula II, characterized in that, wherein the configuration of the carbon atoms marked with "*2" and "*3" is independently R configuration, S configuration or a mixture of the two; R 4 and R 5 each independently is hydrogen or C1-C6alkyl; R 6 and R 7 each independently is C6-C 6-1 substituted with 1, 2, or 3 R 10 substituted aryl; R 6-1 independently halogen, optionally substituted C1-C6alkyl, or 6-1-1 C1-C6alkyl substituted with 1, 2, or 3 R R 6-1-1 independently halogen; R 6-1-2 independently C1-C6alkoxy, hydroxy, or C1-C6alkyl; The compound of Formula II is not Preferably, the compound as shown in formula II satisfies one or more of the following conditions; (1) R 4 and R 5 each independently of one another, C1-C6-alkyl is methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl or sec-butyl; (2) R 6 and R 7 , the C6-C 10 aryl groups in the C6-C 10 aryl groups of R 10 each independently are phenyl or naphthyl; (3) R 6-1 In some embodiments, each of the halogens is independently fluorine, chlorine, bromine, or iodine. (4) R 6-1 In some embodiments, the C1-C6alkyl and C1-C6of the alkyl groups of substituted C1-C6alkyl are independently methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl, or s-butyl. (5) R 6-1-1 In some embodiments, the halogen is independently fluorine, chlorine, bromine, or iodine. (6) R 6-1-2 In some embodiments, the C1-C6alkoxy is independently methoxy, ethoxy, n- propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, or tert-butoxy. (7) R 6-1-2 In some embodiments, each of the C1-C6alkyl groups is independently methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl, or s-butyl. (8) R 6 and R 7 each independently is C6-C 6-1 substituted by 1, 2 or 3 R 10 substituted aryl; (9) R 6-1 independently halogen, C1-C6alkyl substituted by 1, 2, or 3 R 6-1-1 substituted C1-C6alkyl, or Preferably, it is composed of 1, 2, or 3 Rs. 6-1-1 Substituted C1-C6 alkyl groups; (10) R 6-1-2 independently C1-C6alkoxy; (11) the configuration of the carbon atoms marked with "*2" and "*3" is the same, for example, both are R configuration or both are S configuration; (12) the carbon atoms marked with "*2" and "*3" represent an equimolar mixture of the carbon atoms in R configuration and S configuration; Preferably, the compound as shown in formula II satisfies one or more of the following conditions; (1)R 4 It is hydrogen; (2) R 5 Ci-C6-alkyl, for example methyl; (3) R 6 and R 7 each independently is Further preferably, the compound of Formula II is any one of the following structures:

4. A polymeric diamine metal chelate characterized by, The polymeric diamine is a polymeric diamine compound as defined in claim 1 or 2, and the polymeric diamine metal chelate is a chelate formed by chelation of a metal M with -NR 1 R 2 , in particular, it contains one or more structural fragments as shown in formula A: wherein the definitions of "*1", "*", R 1 and R 2 are as described in any of the above aspects. the metal M is a Group VIII transition metal; R is H2O or Cl; D is optionally substituted C6-C10aryl or optionally substituted cyclopentadienyl; and d1 substituted C6-C10aryl or optionally substituted cyclopentadienyl; and 10 substituted C6-C10aryl or optionally substituted cyclopentadienyl; and d2 substituted C6-C10aryl or optionally substituted cyclopentadienyl; and R d1 and R d2 each independently is C1-C6alkyl; Preferably, the polymeric diamine metal chelate satisfies one or more of the following conditions; (1) D, wherein each of the C6-C10aryl and substituted C6-C10aryl groups is independently phenyl or naphthyl; 10 (1) D, wherein each of the C6-C10aryl and substituted C6-C10aryl groups is independently phenyl or naphthyl; 10 (1) D, wherein each of the C6-C10aryl and substituted C6-C10aryl groups is independently phenyl or naphthyl; 10 (1) D, wherein each of the C6-C10aryl and (2) R d1 and R d2 wherein each C1-C6alkyl is independently methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl, or s-butyl; for example, methyl; (3) the R is H2O; (4) said D is optionally substituted cyclopentadienyl; for example, substituted with one or more R d2 substituted cyclopentadienyl; for example, substituted with one or more R d2 substituted cyclopentadienyl; for example, substituted with one or more R (5) the metal M is ruthenium, rhodium or iridium; preferably iridium; (6) in the polymeric diamine metal chelate, the anion paired with the cationic structural fragment as shown in formula A is represented as (X)w, wherein X is a monovalent or divalent anion, w is 1 or 2, when the X is a monovalent anion, the w is 2, when X is a divalent anion, the w is 1; More preferably, when said X is a monovalent anion, said X is a halide anion, such as Cl - ; More preferably, when said X is a divalent anion, said X is SO4 2- ; Preferably, in the polymeric diamine metal chelate, the structural fragment as shown in formula A is 5. A diamine metal chelate characterized by, The diamine metal chelate is a compound as shown in Formula B, wherein the configuration of the carbon atom marked with "*2" and "*3" is independently R configuration, S configuration or a mixture of the two; R 4’ and R 5’ each independently is hydrogen or C1-C6alkyl; R 6’ and R 7’ each independently is C6-C 7-1 substituted with 1, 2, or 3 R 10 substituted aryl; R 7-1 independently halogen, optionally substituted C1-C6alkyl, or 7-1-1 C1-C6alkyl substituted with 1, 2, or 3 R R 7-1-1 independently halogen; R 7-1-2 independently C1-C6alkoxy, hydroxy, or C1-C6alkyl; the definitions of R, D, X, w and metal M are as described in claim 4; the compound of Formula B is not Preferably, the metal chelate of the diamine satisfies one or more of the following conditions: (1) R 4’ and R 5’ wherein each of the C1-C6alkyl groups is independently methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl, or s-butyl; for example, methyl; (2) R 6’ and R 7’ , said C6-C 10 aryl and C6-C 10 aryl in the substituted C6-C 10 aryl are each independently phenyl or naphthyl; (3) R 7-1 In some embodiments, each of the halogens is independently fluorine, chlorine, bromine, or iodine; for example, fluorine, chlorine, or bromine. (4) R 7-1 In some embodiments, the C1-C6alkyl and C1-C6of the substituted C1-C6alkyl groups are independently methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl, or s-butyl; for example, methyl or t-butyl. (5) R 7-1-1 In some embodiments, the halogen is independently fluorine, chlorine, bromine, or iodine; for example, fluorine. (6) R 7-1-2 In some embodiments, the C1-C6alkoxy is independently methoxy, ethoxy, n- propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, or tert-butoxy; e.g., methoxy. (7) R 7-1-2 In some embodiments, each of the C1-C6alkyl groups is independently methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl, or s-butyl. (8) the configurations of the carbon atoms marked with "*2" and "*3" are the same, for example, both are R configuration or both are S configuration; (9) the carbon atoms marked with "*2" and "*3" represent an equimolar mixture of R configuration and S configuration; (10) R 6’ and R 7’ each independently is C6-C 6-1 substituted by 1, 2 or 3 R 10 aryl; (11) R 7-1 independently halogen, C1-C6alkyl substituted by 1, 2, or 3 R 7-1-1 substituted C1-C6alkyl, or Preferably, it is composed of 1, 2, or 3 Rs. 7-1-1 Substituted C1-C6 alkyl groups; (12) R 7-1-2 independently C1-C6alkoxy; Preferably, the metal chelate of the diamine satisfies one or more of the following conditions: (1)R 4’ It is hydrogen; (2) R 5’ is Ci-C6alkyl, for example methyl; (3) R 6’ and R 7’ each independently is Further preferably, the diamine metal chelate is any one of the following structures:

6. Use of a polymeric diamine metal chelate according to claim 4 or a diamine metal chelate according to claim 5 as a catalyst in the asymmetric transfer hydrogenation reaction for the preparation of chiral alcohol compounds; characterized in that ； Preferably, the asymmetric transfer hydrogenation reaction comprises the step of: preparing compound B1 by subjecting compound A1 to the asymmetric transfer hydrogenation reaction described below in the presence of an acid, a substance S, in a solvent; and wherein the configuration of the carbon atom marked with "*4" is independently R configuration, S configuration or a mixture of the two; R 8 substituted C6-Cio aryl, C1-C6 alkyl optionally substituted with 1 or more R 8-1 substituted C6-Cio aryl, C1-C6 alkyl optionally substituted with 1 or more R 10 substituted C6-Cio aryl, C1-C6 alkyl optionally substituted with 1 or more R 8-2 substituted C6-Cio aryl, C1-C6 alkyl optionally substituted with 1 or more R 8-3 substituted C6-Cio aryl, C1-C6 alkyl optionally substituted with 1 or more R 8-4 substituted C6-Cio aryl, C1-C6 alkyl optionally substituted with 1 or more R 8- 5 substituted C6-Cio aryl, C1-C6 alkyl optionally substituted with 1 or more R R 8-1 R 8-2 R 8-3 R 8-4 and R 8-5 Each is independently halogenated, hydroxyl-containing, or optionally coated with one or more R atoms. 8-1-1 Substituted C1-C6 alkyl groups, optionally with one or more R 8-1-2 Substituted C1-C6 alkoxy groups, optionally with one or more R groups 8-1-3 Replacement C6-C 10 The aryl group may be optionally enclosed by one or more R groups. 8-1-3 Substituted C3-C6 cycloalkyl groups; R 8-1-1 and R 8-1-2 is independently halogen; R 8-1-3 independently C1-C6alkyl, C1-C6alkoxy, or halogen; R 9 C1-C6alkyl or C3-C6cycloalkyl, each optionally substituted with 1 or more R 9-1 C1-C6alkyl or C3-C6cycloalkyl, each optionally substituted with 1 or more R R 9-1 independently halogen, cyano or nitro; R 9-2 independently hydroxyl or C1-C6alkoxy; or "R 8-1 and R 9 " or "R 8-5 and R 9 ", taken together with the atom to which they are attached, form a 3-6 membered heterocycloalkenyl optionally substituted with 1, 2, or 3 R 9a ; of the 3-6 membered heterocycloalkenyl groups, 1 or 2 heteroatom groups are present; further comprising 1, 2 or 3 heteroatoms selected from N, O and S; R 9a independently C1-C6alkyl; or R 8 and R 9 with the atom to which they are attached form an optionally substituted 3-6 membered saturated heterocyclic ring, wherein said 3-6 membered saturated heterocyclic ring contains 1 or 2 heteroatom groups 9b substituted with 1, 2, or 3 R further comprising 1, 2 or 3 heteroatoms selected from N, O and S; R 9b independently C1-C6alkyl; the substance S is the polymeric metal chelate of the diamine as described in claim 4 and / or the metal chelate of the diamine as described in claim 5; More preferably, the asymmetric transfer hydrogenation reaction satisfies one or more of the following conditions: (1) the "one or more" is 1, 2 or 3; (2)R 8 In the context, the C6-C 10 aryl and substituted C6-C 10 C6-C in aryl 10 The aryl group can be phenyl or naphthyl independently, for example... (3) R 8 In some embodiments, the C1-C6alkyl and C1-C6of the substituted C1-C6alkyl groups are independently methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl, or s-butyl; for example, (4) R 8 In some embodiments, the C3-C6cycloalkyl and C3-C6cycloalkyl of the substituted C3-C6cycloalkyl is independently cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl. (5) R 8 In the 5-10 membered heteroaryl and the 5-10 membered heteroaryl of the substituted 5-10 membered heteroaryl, the 5-10 membered heteroaryl is independently 1 or 2 heteroatoms selected from O or S, and the 5-10 membered heteroaryl is a 5 membered heteroaryl having 1 heteroatom; for example, (6) R 8-1 , R 8-2 , R 8-3 , R 8-4 , and R 8-5 , wherein each of said halogen is independently fluorine, chlorine, bromine or iodine; (7) R 8-1 In particular, each of the C1-C6alkyl and the C1-C6alkyl of the substituted C1-C6alkyl is independently methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl, or s-butyl, for example methyl or i-propyl. (8) R 8-2 , R 8-3 , R 8-4 , and R 8-5 , wherein the C1-C6alkyl and C1-C6alkyl of substituted C1-C6alkyl are each independently methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl, or s-butyl; (9) R 8-1 In particular, the C1-C6alkyl and substituted C1-C6alkyl of the C1-C6alkyl of the C1-C6alkyl of the C1-C6alkyl of the C1-C6alkyl of the C1-C6alkyl of the C1-C6alkyl of the C1-C6alkyl of the C1-C6alkyl of the C1-C6alkyl of the C1-C6alkyl of the C1-C6alkyl of the C1-C6alkyl of the C1-C6alkyl of the C1-C6alkyl of the C1-C6alkyl of the C1-C6alkyl of the C1-C6alkyl of the C1-C6alkyl of the C1-C6alkyl of the C1-C6alkyl of the (10) R 8-2 , R 8-3 , R 8-4 , and R 8-5 , each of the C1-C6alkoxy and the C1-C6alkoxy in the substituted C1-C6alkoxy is independently methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, or t-butoxy; (11) R 8-1 In particular, the C6-Ci8-aryl and the substituted C6-Ci8-aryl are independently phenyl or naphthyl, for example phenyl. 10 In particular, the C6-Ci8-aryl and the substituted C6-Ci8-aryl are independently phenyl or naphthyl, for example phenyl. 10 In particular, the C6-Ci8-aryl and the substituted C6-Ci8-aryl are independently phenyl or naphthyl, for example phenyl. 10 In particular, the C6-Ci8-aryl (12) R 8-2 (13) R 8-3 (14) R 8-4 (15) R 8-5 (16) R 10 (17) R 10 (18) R 10 (19) R (20) R (21) R (22) R (23) R (24) R (25) R (26) R (27) R (28) R (29) R (30) R (31) R (32) R (33) R (34) R (35) R (36) R (37) R (38) R (39) R (40) R (41 (13) R 8-1 (14) R 8-2 (15) R 8-3 (16) R 8-4 (17) R 8-5 Among the C3-C6cycloalkyl and C3-C6cycloalkyl of the substituted C3-C6cycloalkyl, the C3-C6cycloalkyl is independently cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl, for example cyclohexyl. (14) R 8-1-1 In some embodiments, the halogen is independently fluorine, chlorine, bromine, or iodine; for example, fluorine. (15) R 8-1-2 In some embodiments, the halogen is independently fluorine, chlorine, bromine, or iodine. (16) R 8-1-3 In some embodiments, the C1-C6alkyl is independently methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl, or s-butyl. (17) R 8-1-3 In some embodiments, the C1-C6alkoxy is independently methoxy, ethoxy, n- propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, or tert-butoxy. (18) R 8-1-3 In some embodiments, the halogen is independently fluorine, chlorine, bromine, or iodine. (19) R 9 In some embodiments, the C1-C6alkyl and substituted C1-C6alkyl are independently methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl, or s-butyl; for example, methyl. (20) R 9-1 In some embodiments, the halogen is independently fluorine, chlorine, bromine, or iodine; for example, fluorine. (21) R 9-2 In some embodiments, the C1-C6alkoxy is independently methoxy, ethoxy, n- propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, or tert-butoxy; e.g., methoxy. (22) said 3-6 membered heterocycloalkenyl is independently a 2 heteroatom containing group 5-membered heterocycloalkenyl groups comprising 1 N heteroatom; for example, (23) R 9a In some embodiments, each C1-C6alkyl is independently methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl, or s-butyl; for example, methyl. (24) said 3-6 membered saturated heterocyclic ring is independently a 2-membered heteroatom group a 5-membered heterocycle containing 1 O heteroatom; for example, (25) said R 8 is Ci-C6alkyl, C6-Ci0aryl, or "heteroaryl having 5 to 10 ring members, wherein 1, 2, or 3 of the ring members are selected from N, O, and S, and the number of heteroatoms is 1, 2, or 3"; 8-1 is Ci-C6alkyl, C6-Ci0aryl, or "heteroaryl having 5 to 10 ring members, wherein 1, 2, or 3 of the ring members are selected from N, O, and S, and the number of heteroatoms is 1, 2, or 3"; 10 is Ci-C6alkyl, C6-Ci0aryl, or "heteroaryl having 5 to 10 ring members, wherein 1, or said R 8 and R 9 together with the atom to which they are attached form a 3-6 membered saturated heterocyclic ring substituted with 1, 2, or 3 R 9b substituted with 1 or 2 heteroatom groups further comprising 1, 2 or 3 heteroatoms selected from N, O and S; (26) R 8-1 independently halogen, hydroxy, C1-C6alkoxy, C6-C10aryl, C3-C6cycloalkyl, or C1-C6alkyl optionally substituted with 1 or more R 10 independently halogen, hydroxy, C1-C6alkoxy, C6-C10aryl, C3-C6cycloalkyl, or C1-C6alkyl optionally substituted with 1 or more R 8-1-1 independently halogen, hydroxy, C1-C6alkoxy, C6-C10aryl, C3-C6cycloalkyl, or C1-C6alkyl optionally substituted with 1 or more R or, "R 8-1 and R 9 " together with the atom to which they are attached form a 3-6 membered heterocycloalkenyl substituted with 1, 2, or 3 R 9a In the 3-6 membered heterocycloalkenyl groups, 1 or 2 heteroatom groups are present. further comprising 1, 2 or 3 heteroatoms selected from N, O and S; (27) the substance S is the polymeric diamine metal chelate, and when the configurations of the carbon atoms marked with "*" and "*1" are both R configurations, the compound B1 is (28) the substance S is the polymeric diamine metal chelate, and when the configurations of the carbon atoms marked with "*" and "*1" are both S configurations, the compound B1 is (29) the substance S is the polymeric diamine metal chelate, and when the carbon atoms marked "*" and "*1" indicate that the carbon atoms are an equimolar mixture of the R and S configurations, the compound B1 is an equimolar mixture of R configuration and S configuration; (30) the substance S is the above-mentioned metal chelate of a diamine, the above-mentioned compound B1 is (31) the substance S is the metal chelate of the diamine, wherein the compound B1 is (32) the substance S is the above-mentioned metal chelate of a diamine, and the above-mentioned compound B1 is an equimolar mixture of R configuration and S configuration; (33) the acid is an organic acid, for example R x1 Ci-C6-alkyl; the acid is preferably formic acid; (34) the solvent is a mixed solution of an organic solvent and water; the organic solvent is preferably one or more of aromatic hydrocarbon solvents, alcohol solvents, amide solvents, ether solvents and sulfoxide solvents; further preferably an alcohol solvent or an ether solvent; the alcohol solvent can be methanol; the ether solvent can be 1, 4-dioxane; the water can be deionized water; preferably, the volume ratio of the organic solvent to the water is (1-5):(1-2); preferably 1:1; (35) the molar ratio of the compound A1 to the acid is 1:(3-8); preferably 1:5; (36) the molar ratio of the compound A1 to the polymeric metal chelate of the diamine is 1:(0.0001-0.005); preferably 1:(0.0001-0.0010), further preferably 1:0.0005; (37) the molar ratio of the compound A1 to the metal diamine compound is 1:(0.0005-0.01); preferably 1:(0.001-0.010); preferably 1:0.005; (38) the molar volume ratio of the compound A1 to the solvent is (0.1-0.6) mmol / mL; preferably 0.2 mmol / mL or 0.5 mmol / mL; (39) the reaction temperature of the asymmetric transfer hydrogenation reaction is 40-100°C, preferably 55-70°C; for example, 60°C or 70°C; (40) the reaction time of the asymmetric transfer hydrogenation reaction is 4-24h, preferably 8-20h; for example, 12h; (41) the asymmetric transfer hydrogenation reaction is carried out under inert gas condition; the inert gas can be nitrogen; (42) the asymmetric transfer hydrogenation reaction further comprises the following post-treatment steps: extraction, drying of organic phase, filtration, concentration, purification by silica gel column chromatography, concentration; the extraction can be ethyl acetate extraction three times; the drying of organic phase can be dried with anhydrous sodium sulfate; the eluent in the purification by silica gel column chromatography can be a mixed solvent of dichloromethane and methanol with a volume ratio of 80:1; (43) the reaction raw materials of the asymmetric transfer hydrogenation reaction are the solvent, the acid, the substance S and the compound A1; Preferably, the asymmetric transfer hydrogenation reaction meets one or more of the following conditions: (1) R 8 To (2) R 9 To (3) when "R 8-1 and R 9 , together with the atom to which they are attached, form a 3-6 membered heterocycloalkenyl optionally substituted with 1, 2, or 3 R 9a substituents For wherein n1 and n2 are each independently 0, 1, 2 or 3; (4) when R 8 and R 9 together with the atom to which they are attached form an optionally substituted saturated 3-6 membered heterocyclic ring, said 9b substituted with 1, 2, or 3 R For n3 is 0, 1, 2 or 3; Further preferably, the asymmetric transfer hydrogenation reaction meets one or two of the following conditions: (1) the compound A1 is any one of the following structures: (2) the substance S is the polymeric diamine metal chelate or the diamine metal chelate, in the polymeric diamine metal chelate, the configurations of the carbon atoms marked with "*" and "*1" are both R configurations, in the diamine metal chelate, the configurations of the carbon atoms marked with "*2" and "*3" are both R configurations, and the compound B1 is any one of the following structures:

7. A process for the preparation of compound B1; characterized in that, which comprises the following step: the compound A1 is prepared by asymmetric transfer hydrogenation as described below in the presence of an acid, such as the substance S as described in claim 6, to give the compound B1 ; wherein R8 and R9 are as defined in claim 6; Preferably, the reaction conditions, the ratio of each raw material and the operation method of the asymmetric transfer hydrogenation reaction are as described in the asymmetric transfer hydrogenation reaction of claim 6.

8. A method for producing a polymeric diamine compound, characterized by, It comprises the following steps: compound C is subjected to a polymerization-type reductive coupling reaction in the presence of compound E in a solvent to prepare a polymerization-type diamine compound having a structural framework as shown in formula I; wherein, the configuration of the carbon atom marked with "*5" is independently R configuration, S configuration or a mixture of the two; R 10 R 11 R 12 R 13 R 14 and R 15 Each can be independently selected by 1, 2, or 3 Rs. 10-1 Replacement C6-C 10 aryl; R 10-1 independently C1-C6alkyl; The R mentioned 1 It is hydrogen or a C1-C6 alkyl group; R is hydrogen; and 2 is hydrogen; the polymeric diamine compound and the -L- are as described in any one of claims 1-2; Preferably, the preparation method of the polymeric diamine compound meets one or more of the following conditions: (1) R 10 (2) R 11 (3) R 12 (4) R 13 (5) R 14 (6) R 15 (7) R 10 (8) R 10 (9) R 10 each of the C6-C20aryl groups in the C6-C20aryl and substituted C6-C20aryl groups is independently phenyl or naphthyl; for example, phenyl; (2) R 1 and R 10-1 Among them, the C1-C6 alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl or sec-butyl; for example, methyl; (3) the configuration of the carbon atom marked with "*5" is all R configuration; (4) the configuration of the carbon atom marked with "*5" is all S configuration; (5) the carbon atom marked with "*5" represents an equimolar mixture of R configuration and S configuration; (6) when the configuration of the carbon atom marked with "*5" in compound E is all R configuration, the configuration of the carbon atoms marked with "*" and "*1" in the polymeric diamine compound is also R configuration; when the configuration of the carbon atom marked with "*5" in compound E is S configuration, the configuration of the carbon atoms marked with "*" and "*1" in the polymeric diamine compound is also S configuration; when the carbon atom marked with "*5" in compound E represents an equimolar mixture of R configuration and S configuration, the carbon atoms marked with "*" and "*1" in the polymeric diamine compound represent an equimolar mixture of R configuration and S configuration; (7) in the polymeric reductive coupling reaction, the solvent is an aromatic hydrocarbon solvent and / or an ether solvent; preferably an ether solvent; further preferably diethyl ether and / or tetrahydrofuran; for example, tetrahydrofuran; (8) in the polymeric reductive coupling reaction, the molar ratio of compound C to compound E is 1:(1-1.5); preferably 1:1; (9) in the polymeric reductive coupling reaction, the molar volume ratio of compound C to the solvent is (0.2-0.5) mmol / mL; preferably 0.27 mmol / mL; (10) the reaction temperature of the polymeric reductive coupling reaction is 10-45℃; preferably 25-35℃; (11) the reaction time of the polymeric reductive coupling reaction is 8-48 hours; preferably 24 hours; (12) the polymeric reductive coupling reaction further comprises the following post-treatment steps: adjusting the pH to 2-3 with an acid, washing, adjusting the pH to alkaline with a base, mixing with an organic solvent, filtering, washing the filter cake and drying to obtain the polymeric diamine compound; the acid can be hydrochloric acid, for example 2M dilute hydrochloric acid; the washing can be halogenated hydrocarbon solvent washing, for example dichloromethane washing; the base can be sodium hydroxide, for example 2M sodium hydroxide aqueous solution; the organic solvent can be an alkane solvent, for example n-heptane; the washing of the filter cake can be with halogenated hydrocarbon solvent, alkane solvent and water, for example with dichloromethane, alkane solvent and water; (13) the reaction raw materials of the polymeric reductive coupling reaction are the compound C, the solvent and the compound D; Preferably, the preparation method of the polymeric diamine compound meets one or both of the following conditions; (1) R 10 and R 13 is phenyl; (2) R 11 , R 12 , R 14 , and R 15 are Further preferably, the preparation method of the polymeric diamine compound meets one or both of the following conditions; (1) the compound C is any one of the following structures: (2) the compound E is 9. A polymeric diamine compound prepared by the preparation method of the polymeric diamine compound according to claim 8.

10. A method for preparing a compound as shown in Formula II, characterized in that, which comprises the step of preparing a compound of formula II by reductive coupling of compound F in the presence of compound E in a solvent; wherein R 5 is hydrogen, R 6 is hydrogen, R 4 is as defined in claim 3; and compound E is as defined in claim 8. Preferably, the preparation method of the compound of formula II meets one or more of the following conditions; (1) in the compound E, the configurations of the carbon atoms marked with "*5" are all R configurations; (2) in the compound E, the configurations of the carbon atoms marked with "*5" are all S configurations; (3) the carbon atom marked with "*5" represents an equimolar mixture of R and S configurations; (4) when the configurations of the carbon atoms marked with "*5" in the compound E are all R configurations, the configurations of the carbon atoms marked with "*2" and "*3" in the compound of formula II are also R configurations; when the configurations of the carbon atoms marked with "*5" in the compound E are S configurations, the configurations of the carbon atoms marked with "*2" and "*3" in the compound of formula II are also S configurations; when the carbon atom marked with "*5" in the compound E represents an equimolar mixture of R and S configurations, the carbon atoms marked with "*2" and "*3" in the compound of formula II represent an equimolar mixture of R and S configurations; (5) in the reductive coupling reaction, the solvent is an aromatic hydrocarbon solvent and / or an ether solvent; preferably an ether solvent; further preferably diethyl ether or tetrahydrofuran; for example, tetrahydrofuran; (6) in the reductive coupling reaction, the molar ratio of the compound F to the compound E is 1:(0.5-1.2); preferably 1:0.5; (7) in the reductive coupling reaction, the molar volume ratio of the compound F to the solvent is (0.2-0.5) mmol / mL; preferably 0.4 mmol / mL; (8) the reaction temperature of the reductive coupling reaction is 10-45°C; preferably 25-35°C; (9) the reaction time of the reductive coupling reaction is 8-48 hours; preferably 24 hours; (10) the reductive coupling reaction further comprises the following post-treatment steps: acid adjusting the reaction pH to 2-3, washing, base adjusting the reaction pH to alkaline, extraction, and concentration to obtain a compound as shown in formula II; the acid can be hydrochloric acid, for example 2M dilute hydrochloric acid; the washing can be halogenated hydrocarbon solvent washing, for example dichloromethane washing; the base adjusting the reaction pH to alkaline can be sodium hydroxide, for example 2M sodium hydroxide aqueous solution, pH is 11-12; the extraction can be halogenated hydrocarbon solvent extraction, for example dichloromethane extraction; Preferably, in the process for preparing the compound of Formula II, the compound F is any one of the following structures:

11. A method of preparing the polymeric diamine metal chelate according to claim 4, characterized by, which comprises the following steps: in a solvent, Ia is subjected to metal chelation reaction with a polymeric diamine as described in claim 1 or 2 to prepare a polymeric diamine metal chelate, namely, The Ia is wherein, the definitions of D, X, w and metal M are as described in claim 4; Preferably, the preparation method of the polymeric diamine metal chelate satisfies one or more of the following conditions: (1) in the preparation method of the polymeric diamine metal chelate, the solvent is a mixed solvent of water and an alcohol solvent, for example methanol, and the volume ratio of the water to the alcohol solvent in the mixed solvent is (1-3):1, for example 1:1 or 2:1; (2) in the preparation method of the polymeric diamine metal chelate, the molar ratio of the polymeric diamine to the Ia is (1-5):1, preferably 1:1; (3) in the preparation method of the polymeric diamine metal chelate, the molar volume ratio of the polymeric diamine to the solvent is (0.1-0.6) mmol / mL; preferably 0.25 mmol / mL; (4) in the preparation method of the polymeric diamine metal chelate, the aqueous solution of the Ia is mixed with the alcohol solvent of the polymeric diamine to perform the metal chelation reaction; (5) in the preparation method of the polymeric diamine metal chelate, the aqueous solution of the Ia is added dropwise into the alcohol solvent of the polymeric diamine to perform the metal chelation reaction; (6) the water in the aqueous solution of the Ia and the alcohol solvent in the alcohol solvent of the polymeric diamine are as described in claim 6; (7) the molar concentration of the aqueous solution of the Ia is 0.001-0.1M, for example 0.005M; (8) the molar concentration of the alcohol solvent of the polymeric diamine is 0.001-0.1M, for example 0.005M; (9) in the preparation method of the polymeric diamine metal chelate, the reaction temperature is 10-45℃; preferably 25-35℃; (10) in the preparation method of the polymeric diamine metal chelate, the reaction time is 8-24 hours; preferably 12 hours; (11) in the preparation method of the polymeric diamine metal chelate, the raw materials of the reaction are the solvent, the Ia and the polymeric diamine.

12. A method of preparing a diamine metal chelate, characterized by, which comprises the following steps: in a solvent, Ia is subjected to metal chelation reaction with a diamine compound to prepare a diamine metal chelate; the Ia is as described in claim 11; the diamine compound is a compound as shown in formula II as described in claim 3; Preferably, the method for producing the diamine metal chelate satisfies one or both of the following conditions: (1) In the method for producing the diamine metal chelate, the reaction conditions, the ratio of the raw materials, and the method of operation in the metal chelation reaction are as described in the metal chelation reaction of claim 11. (2) In the method for producing the diamine metal chelate, the raw materials of the reaction are the solvent, the compound of formula Ia, and the diamine compound.

13. Use of a polymeric diamine compound as defined in claim 1 or 2 for the preparation of a polymeric diamine metal chelate as defined in claim 4, characterized in that In the use, the method for producing the polymeric diamine metal chelate is as described in claim 11.

14. Use of a diamine compound according to claim 3 for the preparation of a diamine metal chelate according to claim 5, characterized in that, In the use, the method for producing the diamine metal chelate is as described in claim 12.

15. A single crystal of a compound as shown in Formula XI, characterized in that, The crystal system thereof belongs to an orthorhombic system, a P 21 21 21 space group, and a unit cell parameter of α = β = γ = 90°; Preferably, the single crystal parameters of the compound of Formula X-I are as shown in the table:

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