Preparation method and application of axially chiral indenyl ligand

Abstract

The invention discloses a preparation method and application of axially chiral indenyl ligands, and belongs to the technical field of organic synthesis. According to the preparation method of the axially chiral indenyl ligand, a compound containing an OTf group and a boric acid compound containing an alkoxy group are selected as raw materials, an asymmetric Suzuki-Miyaura cross-coupling reaction is carried out, meanwhile, the reaction efficiency is improved by utilizing a metal catalyst, the enantioselectivity is improved by utilizing a chiral ligand, the axially chiral indenyl ligand is efficiently synthesized through short steps, and the preparation method is simple and easy to implement. The prepared axially chiral indenyl ligand can have relatively high efficiency and excellent performance in transition metal catalysis. The preparation method has the advantages of cheap and easily available materials, simple operation, low equipment requirement, high product yield, no need of complex separation and purification treatment after the reaction, effective improvement of the product quality, and reduction of the cost.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis technology, and in particular to a method for preparing and applying a class of axially chiral indenyl ligands. Background Technology

[0002] The discovery of ferrocene in the 1950s spurred extensive research into novel ligand systems in transition metal coordination chemistry. Among these, the indenyl anion (Ind-) has attracted widespread attention due to its unique electronic properties and high accessibility, characterized by a conjugated cyclopentadiene and benzene ring. Early research on indenyl complexes of pre-transition metals such as titanium and zirconium was relatively in-depth, but in recent years, the focus has gradually shifted to Group 9 metal complexes such as cobalt, rhodium, and iridium, revealing their promising catalytic properties. However, unsubstituted parent indenyl Rh(III) complexes [(η 5 The limited catalytic activity of [-indenyl)RhX2]2 is mainly due to the easy dissociation of the indenyl ligand. Studies have shown that reasonable modification of the indenyl ligand can significantly improve the stability and catalytic performance of the complex, but the development of chiral indenyl metal complexes is still relatively lagging behind.

[0003] Currently, the synthesis of chiral indenyl metal complexes mainly relies on two strategies: chiral resolution and enantiomeric modification. In 2020, the Blakey group synthesized indenyl-Rh(III) complexes using 2-methylindenman-1-one as a starting material, and subsequently achieved chiral resolution by high performance liquid chromatography (HPLC) (Farr, CMB; Kazerouni, AM; Park, B.; Poff, CD; Won, J.; Sharp, KR; Baik, M.-H.; Blakey, SB. Designing a Planar Chiral Rhodium Indenyl Catalyst for Regio-and Enantioselective Allylic C-HAmidation. J. Am. Chem. Soc. 2020, 142, 13996–14004). A representative of the enantiomolecular modification method is the Loginov group, which developed a chiral indene-Rh(III) catalyst using (-)-α-pinene as a raw material (Kharitonov, VB; Podyacheva, E.; Chusov, D.; Nelyubina, YV; Muratov, DV; Loginov, DAPlanarChiral Rhodium Complex Based on the Tetrahydrofluorenyl Core for Enantioselective Catalysis. Org. Lett. 2023, 25, 8906–8911.). In recent years, Wang et al. have also reported the synthesis and application of planar chiral indenyl ligands with the [2.2]benzoindenophane-based (PCP) skeleton (Guo, W.; Jiang, J.; Wang, J. [2.2] Benzoindenophane-Based Chiral Indenyl Ligands: Design, Synthesis, and Applications in Asymmetric C–H Activation. Angew. Chem., Int. Ed. 2024, 63, e202400279.). However, these methods have complex synthetic steps, cumbersome processes, and limited diversity of ligand structures. Therefore, how to provide an efficient synthetic method to expand the application scope and accessibility of chiral indenyl ligands to meet the needs of the asymmetric catalysis field is an urgent problem to be solved in this field. Summary of the Invention

[0004] To address the aforementioned problems in existing technologies, this invention provides a method for preparing and applying a class of axially chiral indenyl ligands. The preparation method of this invention is simple to operate and can efficiently synthesize axially chiral indenyl ligands.

[0005] The technical solution of the present invention is as follows:

[0006] The first aspect of this invention protects a class of axially chiral indenyl ligands, characterized in that the general structural formula of the axially chiral indenyl ligand is shown in Formula 3:

[0007]

[0008] In the formula, R1 includes at least one of cyclohexyl, isopropyl, heptyl, cyclohexylmethyl, 2-cyclopentyl, naphthyl, naphth-2-ylmethyl, substituted or unsubstituted benzyl;

[0009] The substituents on the substituted benzyl group include at least one of methyl and tert-butyl groups;

[0010] The R2 includes at least one of hydrogen atom, methyl, phenyl, isopropyl, tert-butyl, amino, epoxypentane, halogen, trifluoromethyl, and trifluoromethoxy.

[0011] The R3 includes at least one of n-propyl, methyl, benzyl, ethyl, butyl, n-hexyl, cyclohexylmethyl, 4-methylbenzyl, 4-methoxybenzyl, 3,4,5-trimethoxybenzyl, adamantyl, methoxymethyl ether, isopropyl, naphthylmethyl, substituted or unsubstituted phenyl;

[0012] The substituents on the substituted phenyl group include at least one of methyl, tert-butyl, and halogen;

[0013] The R4 includes at least one of hydrogen atom, methoxy group, n-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, and p-methoxyphenyl group.

[0014] The second aspect of this invention protects a method for preparing the axially chiral indene ligand described in the first aspect, comprising the following steps: in the presence of a chiral ligand and a metal catalyst, using compound 1 and compound 2 as raw materials, an asymmetric Suzuki-Miyaura cross-coupling reaction is carried out under alkaline conditions and in a solvent to obtain the axially chiral indene ligand;

[0015] The general structural formula of compound 1 is shown in Formula 1:

[0016]

[0017] In the formula, R3 includes at least one of n-propyl, methyl, benzyl, ethyl, butyl, n-hexyl, cyclohexylmethyl, 4-methylbenzyl, 4-methoxybenzyl, 3,4,5-trimethoxybenzyl, adamantyl, methoxymethyl ether, isopropyl, naphthylmethyl, substituted or unsubstituted phenyl.

[0018] The substituents on the substituted phenyl group include at least one of methyl, tert-butyl, and halogen;

[0019] The R4 includes at least one of hydrogen atom, methoxy group, n-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, and p-methoxyphenyl group;

[0020] The general structural formula of compound 2 is shown in Formula 2:

[0021]

[0022] In the formula, R1 includes at least one of cyclohexyl, isopropyl, heptyl, cyclohexylmethyl, 2-cyclopentyl, naphthyl, naphth-2-ylmethyl, substituted or unsubstituted benzyl; the substituent on the substituted benzyl group includes at least one of methyl and tert-butyl.

[0023] The R2 includes at least one of hydrogen atom, methyl, phenyl, isopropyl, tert-butyl, amino, epoxypentane, halogen, trifluoromethyl, and trifluoromethoxy.

[0024] Preferably, the specific steps include: mixing the compound 1, compound 2, metal catalyst, chiral ligand, base, and solvent, reacting under a protective atmosphere, and then performing post-treatment to obtain the axially chiral indene ligand.

[0025] Preferably, the chiral ligand comprises at least one of (11bR)-N,N-dimethyldinaphthalo[2,1-d:1',2'-f][1,3,2]dioxaphosphatane-4-amine, (R)-(2'-methoxy-[1,1'-binaphthyl]-2-yl)diphenylphosphine, (R)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, (R)-5,5'-bis(diphenylphosphino)-4,4'-bibenzo[d][1,3]dioxacyclopentene, (6,6'-dimethoxy-[1,1'-biphenyl]-2,2'-diyl)bis(diphenylphosphine), and (5,5'-dichloro-6,6'-dimethoxy-[1,1'-biphenyl]-2,2'-diyl)bis(diphenylphosphine);

[0026] And / or, the metal catalyst includes a divalent palladium catalyst.

[0027] Preferably, the divalent palladium catalyst comprises at least one of palladium acetate, palladium chloride, palladium sulfate, palladium nitrate, dichlorobis(triphenylphosphine)palladium, dichlorobis(diphenylphosphinemethane)palladium, dichlorobis(pyridine)palladium, and palladium dibromide;

[0028] And / or, the metal catalyst forms a complex with the chiral ligand, preferably, the complex comprising a complex of palladium chloride and (5,5'-dichloro-6,6'-dimethoxy-[1,1'-biphenyl]-2,2'-diyl)bis(diphenylphosphine).

[0029] Preferably, the alkali includes at least one selected from potassium carbonate, potassium phosphate, cesium carbonate, lithium tert-butoxide, and cesium neopentanoate;

[0030] And / or, the solvent includes at least one of dichloromethane, ethyl acetate, trifluorotoluene, fluorobenzene, 1,4-dioxane, toluene, tetrahydrofuran, 2-methyltetrahydrofuran, and water;

[0031] Preferably, the solvent comprises a mixture of toluene and water; wherein the volume ratio of toluene to water in the mixture is (1-10):1.

[0032] Preferably, the molar ratio of the metal catalyst, chiral ligand, compound 1, and compound 2 is 0.05:(0.05~0.15):(1~2):(1~2).

[0033] Preferably, the molar ratio of the base to compound 1 is (1-4):(1-4).

[0034] Preferably, the reaction temperature is 0–140°C and the reaction time is 24–48 h;

[0035] And / or, the protective atmosphere includes at least one of nitrogen, argon, and helium.

[0036] The third aspect of this invention protects the application of a class of axially chiral indene ligands in the field of catalysis, wherein the axially chiral indene ligand is the axially chiral indene ligand described in the first aspect, and / or the axially chiral indene ligand prepared by the preparation method described in the second aspect.

[0037] The beneficial technical effects of this invention are as follows:

[0038] This invention selects compounds containing OTf groups and boric acid compounds containing alkoxy groups as raw materials to undergo an asymmetric Suzuki-Miyaura cross-coupling reaction. Simultaneously, a metal catalyst is used to improve reaction efficiency, and chiral ligands are used to enhance enantioselectivity. This allows for the efficient synthesis of axially chiral indenyl ligands in a concise and efficient manner, facilitating the rapid construction of novel axially chiral indenyl ligand libraries and corresponding transition metal catalyst libraries. Furthermore, the synthesized axially chiral indenyl ligands exhibit high efficiency and excellent performance in transition metal catalysis. In addition, the preparation method of this invention uses inexpensive and readily available materials, is simple to operate, requires minimal equipment, and yields high product yields. No complex separation and purification processes are needed after the reaction, effectively improving product quality while reducing costs. Attached Figure Description

[0039] Figure 1 The hydrogen spectrum of (S)-2-benzyloxy-1-(2-propyl-1H-indene-3-yl)naphthalene prepared in Example 1 of this invention.

[0040] Figure 2 The carbon spectrum of (S)-2-benzyloxy-1-(2-propyl-1H-indene-3-yl)naphthalene prepared in Example 1 of this invention.

[0041] Figure 3 The photon spectrum of (S)-2-(naphth-1-ylmethoxy)-1-(2-propyl-1H-indene-3-yl)naphthalene prepared in Example 19 of this invention is shown.

[0042] Figure 4 The carbon spectrum of (S)-2-(naphth-1-ylmethoxy)-1-(2-propyl-1H-indene-3-yl)naphthalene prepared in Example 19 of this invention. Detailed Implementation

[0043] The present invention will now be described in detail with reference to the embodiments and accompanying drawings.

[0044] The present invention provides a method for preparing axially chiral indene ligands, comprising the following steps: in the presence of chiral ligands and a metal catalyst, using compound 1 and compound 2 as raw materials, an asymmetric Suzuki-Miyaura cross-coupling reaction is carried out under alkaline conditions and in a solvent to obtain the axially chiral indene ligands.

[0045] In some embodiments, the preparation method includes the following steps: mixing compound 1, compound 2, metal catalyst, chiral ligand, base, and solvent, reacting under a protective atmosphere, and then post-processing to obtain the axially chiral indene ligand.

[0046] In some embodiments, the post-processing includes: removing the solvent under vacuum after the reaction is complete, and purifying the crude product by column chromatography.

[0047] The synthetic route for the axially chiral indenyl ligand is as follows:

[0048]

[0049] The general structural formula of compound 1 is shown in Formula 1:

[0050]

[0051] In the formula, R3 includes at least one of n-propyl, methyl, benzyl, ethyl, butyl, n-hexyl, cyclohexylmethyl, 4-methylbenzyl, 4-methoxybenzyl, 3,4,5-trimethoxybenzyl, adamantyl, methoxymethyl ether, isopropyl, naphthylmethyl, and substituted or unsubstituted phenyl; it is understood that butyl includes at least one of n-butyl and isobutyl.

[0052] The substituents on the substituted phenyl group include at least one of methyl, tert-butyl, and halogen;

[0053] The R4 includes at least one of hydrogen atom, methoxy group, n-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, and p-methoxyphenyl group.

[0054] It is understood that this invention does not limit the preparation method of compound 1, and any preparation method that can achieve the purpose of this invention is within the scope of protection of this invention. For example, compound 1 of this invention can be prepared via the following synthetic route:

[0055]

[0056] The general structural formula of compound 2 is shown in Formula 2:

[0057]

[0058] In the formula, R1 includes at least one of cyclohexyl, isopropyl, heptyl, cyclohexylmethyl, 2-cyclopentyl, naphthyl, naphth-2-ylmethyl, substituted or unsubstituted benzyl; the substituent on the substituted benzyl group includes at least one of methyl and tert-butyl.

[0059] The R2 includes at least one of hydrogen atom, methyl, phenyl, isopropyl, tert-butyl, amino, epoxypentane, halogen, trifluoromethyl, and trifluoromethoxy.

[0060] It is understood that this invention does not limit the preparation method of compound 2, and any preparation method that can achieve the purpose of this invention is within the scope of protection of this invention. In the following examples and comparative examples, compound 2 was purchased.

[0061] In some embodiments, the metal catalyst includes a divalent palladium catalyst.

[0062] In some embodiments, the metal catalyst forms a complex with the chiral ligand and is then mixed with compound 1, compound 2, a base, and a solvent.

[0063] In some embodiments, the complex comprises a complex of palladium chloride and (5,5'-dichloro-6,6'-dimethoxy-[1,1'-biphenyl]-2,2'-diyl)bis(diphenylphosphine) ([PdCl2·L6]).

[0064] The synthetic route for the above complex [PdCl2·L6] is as follows:

[0065]

[0066] This invention selects an indene precursor containing an OTf group and naphthylboronic acid containing an alkoxy group as raw materials to undergo an asymmetric Suzuki-Miyaura cross-coupling reaction. A catalyst is then used to improve the reaction efficiency, and chiral ligands are used to improve the enantioselectivity, thereby obtaining axially chiral indene ligands in high yield.

[0067] The catalysts and chiral ligands used in the following examples and comparative examples of the present invention are all commercially available.

[0068] Example 1: Preparation of (S)-2-benzyloxy-1-(2-propyl-1H-inden-3-yl)naphthalene

[0069] The synthetic route for (S)-2-benzyloxy-1-(2-propyl-1H-inden-3-yl)naphthalene is as follows:

[0070]

[0071] The preparation method of (S)-2-benzyloxy-1-(2-propyl-1H-inden-3-yl)naphthalene is as follows:

[0072] 2-propyl-1H-inden-3-yltrifluoromethanesulfonate (0.1 mmol, 30.6 mg), (2-(benzyloxy)naphth-1-yl)boronic acid (0.2 mmol, 55.6 mg), [PdCl2·L6] (4.0 mg, 0.005 mmol, 5.0 mmol%), and potassium phosphate (K3PO4, 42.5 mg, 0.2 mmol) were added to a 25 mL Shrek tube with a diaphragm. The system was evacuated and purged with argon gas, and this operation was repeated three times. Then, toluene (0.8 mL) and water (0.2 mL) were added, and the mixture was stirred at 25 °C for 48.0 h. After the reaction was completed, the solvent was removed under vacuum, and the crude product was purified by column chromatography (eluting solution of 0.5% ethyl acetate in petroleum ether) to obtain 32.4 mg of (S)-2-benzyloxy-1-(2-propyl-1H-inden-3-yl)naphthalene, with a yield of 82% and an enantiomeric excess of 95%.

[0073] Using nuclear magnetic resonance hydrogen spectroscopy (NMR) 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The product obtained in this embodiment was analyzed by C NMR.

[0074] 1 H NMR (500MHz, CDCl3) δ7.92–7.83(m,2H),7.63–7.57(m,1H),7.54–7.49(m,1H),7.41(d,J=9.0Hz,1H),7.39–7.31(m,2H),7.25–7.20(m,3H),7.1 9–7.11(m,4H),6.84–6.76(m,1H),5.13(d,J=12.5Hz,1H),5.09(d,J=12 .5Hz,1H),3.63(d,J=22.5Hz,1H),3.61(d,J=22.5Hz,1H),1.95(s,3H).

[0075] 13 C NMR (126MHz, CDCl3) δ153.0,146.3,142.4,141.4,136.5,132.7,132.4,128.5,128.1,127.2,1 26.9,126.5,125.9,125.2,125.0,124.6,122.8,122.6,122.1,118.8,115.3,70.7,41.9,14.3.

[0076] 1H NMR spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 C NMR data confirm that the product obtained in this embodiment is (S)-2-benzyloxy-1-(2-propyl-1H-indene-3-yl)naphthalene.

[0077] Example 2: (S)-2-(benzyloxy)-1-(2-methyl-1H-inden-3-yl)naphthalene

[0078] The synthetic route for (S)-2-(benzyloxy)-1-(2-methyl-1H-inden-3-yl)naphthalene is as follows:

[0079]

[0080] The preparation method of (S)-2-(benzyloxy)-1-(2-methyl-1H-inden-3-yl)naphthalene is as follows:

[0081] 2-Methyl-1H-inden-3-yltrifluoromethanesulfonate (0.1 mmol, 27.8 mg), (2-(benzyloxy)naphth-1-yl)boronic acid (0.2 mmol, 55.6 mg), [PdCl2·L6] (4.0 mg, 0.005 mmol, 5.0 mmol%), and potassium phosphate (K3PO4, 42.5 mg, 0.2 mmol) were added to a 25 mL Shrek tube with a diaphragm. The system was evacuated and purged with argon gas, and this operation was repeated three times. Then, toluene (0.8 mL) and water (0.2 mL) were added, and the mixture was stirred at 25 °C for 48.0 h. After the reaction was completed, the solvent was removed under vacuum, and the crude product was purified by column chromatography (eluting buffer was petroleum ether solution of 0.5% ethyl acetate) to obtain 33.0 mg (S)-2-(benzyloxy)-1-(2-methyl-1H-inden-3-yl)naphthalene, with a yield of 91% and an enantiomeric excess of 79%.

[0082] Using nuclear magnetic resonance hydrogen spectroscopy (NMR) 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The product obtained in this embodiment was analyzed by C NMR.

[0083] 1 H NMR (500MHz, CDCl3) δ7.92–7.83(m,2H),7.63–7.57(m,1H),7.54–7.49(m,1H),7.41(d,J=9.0Hz,1H),7.39–7.31(m,2H),7.25–7.20(m,3H),7.1 9–7.11(m,4H),6.84–6.76(m,1H),5.13(d,J=12.5Hz,1H),5.09(d,J=12 .5Hz,1H),3.63(d,J=22.5Hz,1H),3.61(d,J=22.5Hz,1H),1.95(s,3H).

[0084] 13 C NMR (126MHz, CDCl3) δ153.0,146.3,142.4,141.4,136.5,132.7,132.4,128.5,128.1,127.2,1 26.9,126.5,125.9,125.2,125.0,124.6,122.8,122.6,122.1,118.8,115.3,70.7,41.9,14.3.

[0085] 1H NMR spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13C NMR data confirm that the product obtained in this embodiment is (S)-2-(benzyloxy)-1-(2-methyl-1H-indene-3-yl)naphthalene.

[0086] Example 3: Preparation of (S)-2-(benzyloxy)-1-(2-ethyl-1H-inden-3-yl)naphthalene

[0087] The synthetic route for (S)-2-(benzyloxy)-1-(2-ethyl-1H-inden-3-yl)naphthalene is as follows:

[0088]

[0089] The preparation method of (S)-2-(benzyloxy)-1-(2-ethyl-1H-inden-3-yl)naphthalene is as follows:

[0090] 2-Ethyl-1H-inden-3-yl trifluoromethanesulfonate (0.1 mmol, 29.2 mg), (2-(benzyloxy)naphth-1-yl)boronic acid (0.2 mmol, 55.6 mg), [PdCl2·L6] (4.0 mg, 0.005 mmol, 5.0 mmol%), and potassium phosphate (K3PO4, 42.5 mg, 0.2 mmol) were added to a 25 mL Shrek tube with a diaphragm. The system was evacuated and purged with argon gas, and this operation was repeated three times. Then, toluene (0.8 mL) and water (0.2 mL) were added, and the mixture was stirred at 25 °C for 48.0 hours. After the reaction was completed, the solvent was removed under vacuum, and the crude product was purified by column chromatography (eluting solution of 0.5% ethyl acetate in petroleum ether) to give 29.0 mg (S)-2-(benzyloxy)-1-(2-ethyl-1H-inden-3-yl)naphthalene, with a yield of 77% and an enantiomeric excess of 85%.

[0091] Using nuclear magnetic resonance hydrogen spectroscopy (NMR) 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The product obtained in this embodiment was analyzed by C NMR.

[0092] 1H NMR (500MHz, CDCl3) δ7.89–7.81(m,2H),7.60(dd,J=8.5,1.5Hz,1H),7.53(dd,J=6.5,1. 5Hz,1H),7.39(d,J=9.0Hz,1H),7.38–7.30(m,2H),7.23(qd,J=4.0,2.0Hz,3H),7.19–7.1 1(m,4H),6.77(dd,J=7.0,1.5Hz,1H),5.12(d,J=12.5Hz,1H),5.08(d,J=12.5Hz,1H),3.6 6(d,J=22.5Hz,1H), 3.63(d,J=22.5Hz,1H), 2.33(q,J=7.5Hz,2H), 1.07(t,J=7.5Hz,3H).

[0093] 13 C NMR (126MHz, CDCl3) δ154.1,149.3,147.5,142.6,137.7,133.7,132.9,129.6,129.2,128.4,128.1,1 27.6,127.0,126.3,126.2,125.8,124.0,123.8,123.4,120.1,120.0,116.5,71.8,40.2,23.0,13.8.

[0094] 1H NMR spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 C NMR data confirm that the product obtained in this embodiment is (S)-2-(benzyloxy)-1-(2-ethyl-1H-indene-3-yl)naphthalene.

[0095] Example 4: Preparation of (S)-2-(benzyloxy)-1-(2-butyl-1H-inden-3-yl)naphthalene

[0096] The synthetic route for (S)-2-(benzyloxy)-1-(2-butyl-1H-inden-3-yl)naphthalene is as follows:

[0097]

[0098] The preparation method of (S)-2-(benzyloxy)-1-(2-butyl-1H-inden-3-yl)naphthalene is as follows:

[0099] Add 2-butyl-1H-inden-3-yltrifluoromethanesulfonate (0.1 mmol, 32.0 mg), (2-(benzyloxy)naphth-1-yl)boronic acid (0.2 mmol, 55.6 mg), [PdCl2·L6] (4.0 mg, 0.005 mmol, 5.0 mmol%), and potassium phosphate (K3PO4, 42.5 mg, 0.2 mmol) to a septum. Evacuate the system and purge with argon gas. Repeat this process three times. Then add toluene (0.8 mL) and water (0.2 mL) and stir the mixture at 25 °C for 48.0 hours. After the reaction was completed, the solvent was removed under vacuum, and the crude product was purified by column chromatography (eluting solution of 0.5% ethyl acetate in petroleum ether) to obtain 25.5 mg (S)-2-(benzyloxy)-1-(2-butyl-1H-inden-3-yl)naphthalene, with a yield of 63% and an enantiomeric excess of 92%.

[0100] Using nuclear magnetic resonance hydrogen spectroscopy (NMR) 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The product obtained in this embodiment was analyzed by C NMR.

[0101] 1 H NMR (500MHz, CDCl3) δ7.85 (t, J=8.0Hz, 2H), 7.60 (dd, J=8.5, 1.5Hz, 1H), 7.53 (d, J=7 .0Hz,1H),7.39(d,J=9.0Hz,1H),7.36–7.30(m,2H),7.25–7.21(m,3H),7.19–7.08(m, 4H),6.79–6.74(m,1H),5.15–5.06(m,2H),3.67(d,J=22.5Hz,1H),3.60(d,J=22.5Hz ,1H),2.38–2.24(m,2H),1.53–1.42(m,2H),1.25–1.14(m,2H),0.73(t,J=7.5Hz,3H).

[0102] 13 C NMR (126MHz, CDCl3) δ154.1,148.2,147.5,142.6,137.8,133.7,133.5,129.6,129.2,128.4,128.0,127.6,1 27.0,126.3,126.2,125.8,123.9,123.8,123.4,119.98,119.96,116.3,71.6,40.7,31.5,29.6,22.8,14.0.

[0103] 1H NMR spectrum ( 1H NMR) and carbon nuclear magnetic resonance (NMR) 13 C NMR data confirm that the product obtained in this embodiment is (S)-2-(benzyloxy)-1-(2-butyl-1H-indene-3-yl)naphthalene.

[0104] Example 5: Preparation of (S)-2-(benzyloxy)-1-(2-cyclohexylmethyl-1H-inden-3-yl)naphthalene

[0105] The synthetic route for (S)-2-(benzyloxy)-1-(2-cyclohexylmethyl-1H-inden-3-yl)naphthalene is as follows:

[0106]

[0107] The preparation method of (S)-2-(benzyloxy)-1-(2-cyclohexylmethyl-1H-inden-3-yl)naphthalene is as follows:

[0108] Add 2-(cyclohexylmethyl)-1H-inden-3-yltrifluoromethanesulfonate (0.1 mmol, 36.0 mg), (2-(benzyloxy)naphth-1-yl)boronic acid (0.2 mmol, 55.6 mg), [PdCl2·L6] (4.0 mg, 0.005 mmol, 5.0 mmol%), and potassium phosphate (K3PO4, 42.5 mg, 0.2 mmol) to a septum. Evacuate the system and purge with argon gas. Repeat this process three times. Then add toluene (0.8 mL) and water (0.2 mL), and stir the mixture at 25 °C for 48.0 hours. After the reaction was completed, the solvent was removed under vacuum, and the crude product was purified by column chromatography (eluting buffer was petroleum ether solution of 0.5% ethyl acetate) to obtain 32.9 mg (S)-2-(benzyloxy)-1-(2-cyclohexylmethyl-1H-inden-3-yl)naphthalene, with a yield of 74% and an enantiomeric excess of 97%.

[0109] Using nuclear magnetic resonance hydrogen spectroscopy (NMR) 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The product obtained in this embodiment was analyzed by C NMR.

[0110] 1H NMR(500MHz, CDCl3)δ7.78–7.72(m,2H),7.50(dd,J=8.0,1.5Hz,1H),7.44–7.40(m,1H),7.28(d,J=9.0Hz,2H),7.2 7–7.20(m,1H),7.17–7.11(m,3H),7.10–7.00(m,4H),6.65(dd,J=7.0,2.0Hz,1H),5.05–4.96(m,2H),3.56(d,J=22. 5Hz,1H),3.48(d,J=22.5Hz,1H),2.15–2.04(m,2H),1.57–1.48(m,1H),1.47–1.39(m,3H),1.26–1.16(m,1H),1.00( tdq,J=12.5,9.5,3.0Hz,2H),0.89(tt,J=12.5,3.0Hz,1H),0.62(tdd,J=12.5,11.0,3.0Hz,1H),0.56–0.48(m,1H).

[0111] 13 C NMR (126MHz, CDCl3) δ154.1,147.5,147.2,142.6,137.9,134.5,133.6,129.5,129.2,128.4,128.0,127.5,126.9,126. 22,126.21,125.9,123.9,123.8,123.3,119.95,119.91,116.2,71.6,41.1,38.1,37.7,33.5,33.4,26.5,26.40,26.38.

[0112] 1H NMR spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 C NMR data confirm that the product obtained in this embodiment is (S)-2-(benzyloxy)-1-(2-cyclohexylmethyl-1H-indene-3-yl)naphthalene.

[0113] Example 6: Preparation of (S)-1-(2-benzyl-1H-inden-3-yl)-2-(benzyloxy)naphthalene

[0114] The synthetic route for (S)-1-(2-benzyl-1H-inden-3-yl)-2-(benzyloxy)naphthalene is as follows:

[0115]

[0116] The preparation method of (S)-1-(2-benzyl-1H-inden-3-yl)-2-(benzyloxy)naphthalene is as follows:

[0117] Add 2-benzyl-1H-inden-3-yl trifluoromethanesulfonate (0.1 mmol, 35.4 mg), (2-(benzyloxy)naphth-1-yl)boronic acid (0.2 mmol, 55.6 mg), [PdCl2·L6] (4.0 mg, 0.005 mmol, 5.0 mmol%), and potassium phosphate (K3PO4, 42.5 mg, 0.2 mmol) to a septum. Evacuate the system and purge with argon gas. Repeat this process three times. Then add toluene (0.8 mL) and water (0.2 mL) and stir the mixture at 25 °C for 48.0 hours. After the reaction was completed, the solvent was removed under vacuum, and the crude product was purified by column chromatography (elution buffer was petroleum ether solution of 0.5% ethyl acetate) to obtain 42.5 mg (S)-1-(2-benzyl-1H-inden-3-yl)-2-(benzyloxy)naphthalene, with a yield of 97% and an enantiomeric excess of 90%.

[0118] Using nuclear magnetic resonance hydrogen spectroscopy (NMR) 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The product obtained in this embodiment was analyzed by C NMR.

[0119] 1 H NMR (500MHz, CDCl3) δ7.98–7.86(m,2H),7.73–7.66(m,1H),7.52–7.32(m,4H),7.27(dq,J=5.0,3.0Hz,3H),7.22(dd,J=7.0,3 .0Hz,2H),7.19–7.08(m,7H),6.83(dd,J=7.0,2.0Hz,1H),5.17(d,J=2.5Hz,2H),3.65(d,J=2.0Hz,2H),3.53(d,J=2.5Hz,2H).

[0120] 13 C NMR (126MHz, CDCl3) δ154.3,147.1,146.3,142.9,140.7,137.7,134.7,133.8,129.6,129.5,129.1,128.5,128. 3,128.2,127.7,127.0,126.5,126.3,126.0,125.7,124.2,124.0,123.5,120.7,120.3,116.1,71.6,40.6,36.3.

[0121] 1H NMR spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13C NMR data confirm that the product obtained in this embodiment is (S)-1-(2-benzyl-1H-indene-3-yl)-2-(benzyloxy)naphthalene.

[0122] Example 7: Preparation of (S)-2-(benzyloxy)-1-(2-(3,4,5-trimethoxybenzyl)-1H-inden-3-yl)naphthalene

[0123] The synthetic route for (S)-2-(benzyloxy)-1-(2-(3,4,5-trimethoxybenzyl)-1H-inden-3-yl)naphthalene is as follows:

[0124]

[0125] The preparation method of (S)-2-(benzyloxy)-1-(2-(3,4,5-trimethoxybenzyl)-1H-inden-3-yl)naphthalene is as follows:

[0126] Add 2-(3,4,5-trimethoxybenzyl)-1H-inden-3-yltrifluoromethanesulfonate (0.1 mmol, 44.4 mg), (2-(benzyloxy)naphth-1-yl)boronic acid (0.2 mmol, 55.6 mg), [PdCl2·L6] (4.0 mg, 0.005 mmol, 5.0 mmol%), and potassium phosphate (K3PO4, 42.5 mg, 0.2 mmol) to a septum. Evacuate the system and purge with argon gas. Repeat this process three times. Then add toluene (0.8 mL) and water (0.2 mL) and stir the mixture at 25 °C for 48.0 hours. After the reaction was completed, the solvent was removed under vacuum, and the crude product was purified by column chromatography (eluting buffer was 5.0% ethyl acetate in petroleum ether) to give 52.8 mg (S)-2-(benzyloxy)-1-(2-(3,4,5-trimethoxybenzyl)-1H-inden-3-yl)naphthalene, with a yield of 99% and an enantiomeric excess of 90%.

[0127] Using nuclear magnetic resonance hydrogen spectroscopy (NMR) 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The product obtained in this embodiment was analyzed by C NMR.

[0128] 1H NMR (500MHz, CDCl3) δ7.90 (d, J=9.0Hz, 1H), 7.87 (dd, J=7.5, 1.6Hz, 1H), 7.66 (dd, J=8.5, 1.5Hz, 1H),7.50(d,J=7.0Hz,1H),7.44(d,J=9.0Hz,1H),7.41–7.36(m,1H),7.36–7.31(m,1H),7.25–7. 21(m,3H),7.21–7.13(m,4H),6.82(dd,J=7.0,1.5Hz,1H),6.24(s,2H),5.16(d,J=12.5Hz,1H),5 .12(d,J=12.5Hz,1H),3.76(s,3H),3.62(d,J=15.0Hz,2H),3.58(s,6H),3.54(d,J=15.0Hz,2H).

[0129] 13 C NMR (126MHz, CDCl3) δ154.2,153.1,147.0,146.2,142.8,137.5,136.3,136.1,134.7,133.7,129.6,129.6,128.4,128 .2,127.7,127.0,126.5,126.4,125.7,124.3,124.0,123.6,120.3,119.4,116.2,105.7,71.8,60.9,55.9,40.8,36.6.

[0130] 1H NMR spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 C NMR data confirm that the product obtained in this embodiment is (S)-2-(benzyloxy)-1-(2-(3,4,5-trimethoxybenzyl)-1H-indene-3-yl)naphthalene.

[0131] Example 8: Preparation of (S)-(3r,5r,7r)-1-((3-(2-(benzyloxy)naphth-1-yl)-1H-inden-2-yl)methyl)adamantane

[0132] The synthetic route for (S)-(3r,5r,7r)-1-((3-(2-(benzyloxy)naphth-1-yl)-1H-inden-2-yl)methyl)adamantane is as follows:

[0133]

[0134] Add 2-(((1s,3s)-adamantane-1-yl)methyl)-1H-inden-3-yltrifluoromethanesulfonate (0.1 mmol, 41.2 mg), (2-(benzyloxy)naphth-1-yl)boronic acid (0.2 mmol, 55.6 mg), [PdCl2·L6] (4.0 mg, 0.005 mmol, 5.0 mmol%), and potassium phosphate (K3PO4, 42.5 mg, 0.2 mmol) to a 25 mL Shrek tube with a diaphragm. Evacuate the system and purge with argon gas. Repeat this operation three times. Then add toluene (0.8 mL) and water (0.2 mL), and stir the mixture at 25 °C for 48.0 hours. After the reaction was completed, the solvent was removed under vacuum, and the crude product was purified by column chromatography (eluting buffer was petroleum ether solution of 0.5% ethyl acetate) to give 30.3 mg (S)-(3r,5r,7r)-1-((3-(2-(benzyloxy)naphth-1-yl)-1H-inden-2-yl)methyl)adamantane, with a yield of 61% and an enantiomeric excess of >99%.

[0135] Using nuclear magnetic resonance hydrogen spectroscopy (NMR) 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The product obtained in this embodiment was analyzed by C NMR.

[0136] 1 H NMR (500MHz, CDCl3) δ7.86–7.80(m,2H),7.57(dd,J=8.0,1.5Hz,1H),7.49(d,J=7.0Hz,1H),7.35(d ,J=9.0Hz,1H),7.33–7.28(m,2H),7.25–7.16(m,5H),7.12(dtd,J=18.0,7.5,1.5Hz,2H),6.75–6.7 1(m,1H),5.08(s,2H),3.74(d,J=22.5Hz,1H),3.67(d,J=22.5Hz,1H),2.20(d,J=13.5Hz,1H),2.08 (d,J=13.5Hz,1H),1.76(p,J=3.0Hz,3H),1.58–1.48(m,4H),1.46–1.38(m,4H),1.38–1.30(m,4H).

[0137] 13C NMR (126MHz, CDCl3) δ154.1,147.2,145.2,143.0,137.9,135.9,133.4,129.5,129.2,128.4,128.0,127.5,126 .7,126.2,126.1,126.0,123.8,123.8,123.1,120.13,120.08,115.8,71.4,44.8,44.5,43.1,37.0,34.8,28.9.

[0138] 1H NMR spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 C NMR data confirm that the product obtained in this embodiment is (S)-(3r,5r,7r)-1-((3-(2-(benzyloxy)naphth-1-yl)-1H-indene-2-yl)methyl)adamantane.

[0139] Example 9: Preparation of (S)-2-(benzyloxy)-1-(6-(tert-butyl)-2-propyl-1H-inden-3-yl)naphthalene

[0140] The synthetic route for (S)-2-(benzyloxy)-1-(6-(tert-butyl)-2-propyl-1H-inden-3-yl)naphthalene is as follows:

[0141]

[0142] The preparation method of (S)-2-(benzyloxy)-1-(6-(tert-butyl)-2-propyl-1H-inden-3-yl)naphthalene is as follows:

[0143] Add 6-(tert-butyl)-2-propyl-1H-inden-3-yltrifluoromethanesulfonate (0.1 mmol, 36.2 mg), (2-(benzyloxy)naphth-1-yl)boronic acid (0.2 mmol, 55.6 mg), [PdCl2·L6] (4.0 mg, 0.005 mmol, 5.0 mmol%), and potassium phosphate (K3PO4, 42.5 mg, 0.2 mmol) to a septum. Evacuate the system and purge with argon gas. Repeat this process three times. Then add toluene (0.8 mL) and water (0.2 mL) and stir the mixture at 25 °C for 48.0 hours. After the reaction was completed, the solvent was removed under vacuum, and the crude product was purified by column chromatography (eluting buffer was petroleum ether solution of 0.5% ethyl acetate) to give 42.4 mg (S)-2-(benzyloxy)-1-(6-(tert-butyl)-2-propyl-1H-inden-3-yl)naphthalene, with a yield of 95% and an enantiomeric excess of 91%.

[0144] Using nuclear magnetic resonance hydrogen spectroscopy (NMR) 1H NMR) and carbon nuclear magnetic resonance (NMR) 13 The product obtained in this embodiment was analyzed by C NMR.

[0145] 1 H NMR (500MHz, CDCl3) δ7.77–7.72(m,2H),7.54(dd,J=8.0,1.5Hz,1H),7.48(d,J=2.0Hz,1H ),7.28(d,J=9.0Hz,1H),7.26–7.19(m,2H),7.12(dd,J=5.0,2.0Hz,3H),7.06(ddd,J=7.0, 3.5,2.0Hz,3H),6.59(d,J=8.0Hz,1H),5.08–4.91(m,2H),3.62–3.51(m,1H),3.51–3.43( m,1H),2.17(td,J=8.0,4.0Hz,2H),1.46–1.38(m,2H),1.28(s,9H),0.68(t,J=7.5Hz,3H).

[0146] 13 C NMR (126MHz, CDCl3) δ154.0,147.2,146.7,144.8,142.3,137.7,133.6,133.2,129.5,128.9,128.2,127.9,12 7.4,126.9,126.1,125.9,123.8,123.1,120.4,120.2,119.3,116.2,71.5,40.6,34.6,31.9,31.8,22.5,14.2.

[0147] 1H NMR spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 C NMR data confirm that the product obtained in this embodiment is (S)-2-(benzyloxy)-1-(6-(tert-butyl)-2-propyl-1H-indene-3-yl)naphthalene.

[0148] Example 10: Preparation of (S)-2-(benzyloxy)-1-(5-methoxy-2-propyl-1H-inden-3-yl)naphthalene

[0149] The synthetic route for (S)-2-(benzyloxy)-1-(5-methoxy-2-propyl-1H-inden-3-yl)naphthalene is as follows:

[0150]

[0151] The preparation method of (S)-2-(benzyloxy)-1-(5-methoxy-2-propyl-1H-inden-3-yl)naphthalene is as follows:

[0152] Add 5-methoxy-2-propyl-1H-inden-3-yltrifluoromethanesulfonate (0.1 mmol, 33.6 mg), (2-(benzyloxy)naphth-1-yl)boronic acid (0.2 mmol, 55.6 mg), [PdCl2·L6] (4.0 mg, 0.005 mmol, 5.0 mmol%), and potassium phosphate (K3PO4, 42.5 mg, 0.2 mmol) to a septum. Evacuate the system and purge with argon gas. Repeat this process three times. Then add toluene (0.8 mL) and water (0.2 mL), and stir the mixture at 25 °C for 48.0 hours. After the reaction was completed, the solvent was removed under vacuum, and the crude product was purified by column chromatography (eluting buffer was 1.0% ethyl acetate in petroleum ether) to give 24.0 mg (S)-2-(benzyloxy)-1-(5-methoxy-2-propyl-1H-inden-3-yl)naphthalene, with a yield of 57% and an enantiomeric excess of 91%.

[0153] Using nuclear magnetic resonance hydrogen spectroscopy (NMR) 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The product obtained in this embodiment was analyzed by C NMR.

[0154] 1 H NMR (500MHz, CDCl3) δ7.84 (t, J=8.5Hz, 2H), 7.59 (d, J=8.0Hz, 1H), 7.38 (dd, J=8. 5,6.0Hz,2H),7.33(t,J=9.0Hz,2H),7.23(d,J=7.0Hz,3H),7.18(d,J=7.5Hz,2H), 6.76–6.66(m,1H),6.34–6.26(m,1H),5.16–5.04(m,2H),3.63(s,3H),3.60–3.49( m,2H),2.26(t,J=8.0Hz,2H),1.49(dq,J=13.5,6.5Hz,2H),0.77(t,J=7.5Hz,3H).

[0155] 13 C NMR (126MHz, CDCl3) δ159.0,154.1,149.7,149.0,137.8,134.8,133.7,133.6,129.6,129.2,128.4,128.0, 127.6,127.0,126.3,125.8,124.0,123.7,119.9,116.3,109.8,105.8,71.6,55.6,39.9,32.1,22.5,14.3.

[0156] 1H NMR spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 C NMR data confirm that the product obtained in this embodiment is (S)-2-(benzyloxy)-1-(5-methoxy-2-propyl-1H-indene-3-yl)naphthalene.

[0157] Example 11: Preparation of (S)-2-(benzyloxy)-6-butyl-1-(2-propyl-1H-inden-3-yl)naphthalene

[0158] The synthetic route for (S)-2-(benzyloxy)-6-butyl-1-(2-propyl-1H-inden-3-yl)naphthalene is as follows:

[0159]

[0160] The preparation method of (S)-2-(benzyloxy)-6-butyl-1-(2-propyl-1H-inden-3-yl)naphthalene is as follows:

[0161] 2-propyl-1H-inden-3-yltrifluoromethanesulfonate (0.1 mmol, 30.6 mg), (2-(benzyloxy)-6-butylnaphth-1-yl)boronic acid (0.2 mmol, 66.8 mg), [PdCl2·L6] (4.0 mg, 0.005 mmol, 5.0 mmol%), and potassium phosphate (K3PO4, 42.5 mg, 0.2 mmol) were added to a 25 mL Shrek tube with a diaphragm. The system was evacuated and purged with argon gas, and this operation was repeated three times. Then, toluene (0.8 mL) and water (0.2 mL) were added, and the mixture was stirred at 25 °C for 48.0 hours. After the reaction was completed, the solvent was removed under vacuum, and the crude product was purified by column chromatography (eluting buffer was petroleum ether solution of 1.0% ethyl acetate) to give 34.8 mg (S)-2-(benzyloxy)-6-butyl-1-(2-propyl-1H-inden-3-yl)naphthalene, with a yield of 78% and an enantiomeric excess of 91%.

[0162] Using nuclear magnetic resonance hydrogen spectroscopy (NMR) 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The product obtained in this embodiment was analyzed by C NMR.

[0163] 1H NMR (400MHz, CDCl3) δ7.68(d,J=9.0Hz,1H),7.51(d,J=2.0Hz,1H),7.48–7.39(m,2H),7.25(d,J=9.0Hz,1H ),7.12(dd,J=5.5,2.0Hz,3H),7.10–7.00(m,5H),6.72–6.59(m,1H),4.99(d,J=12.5Hz,1H),4.95(d,J=12 .5Hz,1H),3.56(d,J=28.0Hz,1H),3.48(d,J=28.0Hz,1H),2.71–2.58(m,2H),2.19(td,J=8.0,2.0Hz,2H), 1.66–1.52(m,2H),1.46–1.39(m,2H),1.31(h,J=7.5Hz,2H),0.86(t,J=7.5Hz,3H),0.69(t,J=7.5Hz,3H).

[0164] 13 C NMR (101MHz, CDCl3) δ153.6,147.9,147.5,142.6,138.4,137.9,133.7,132.1,129.8,128.6,128.3,127.9,127. 5,127.0,126.4,126.2,125.7,123.8,123.4,120.0,116.5,71.9,40.6,35.7,33.6,32.0,22.6,22.6,14.3,14.1.

[0165] 1H NMR spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 C NMR data confirm that the product obtained in this embodiment is (S)-2-(benzyloxy)-6-butyl-1-(2-propyl-1H-indene-3-yl)naphthalene.

[0166] Example 12: Preparation of (S)-2-(heptoxy)-1-(2-propyl-1H-inden-3-yl)naphthalene

[0167] The synthetic route for (S)-2-(heptoxy)-1-(2-propyl-1H-inden-3-yl)naphthalene is as follows:

[0168]

[0169] The preparation method of (S)-2-(heptoxy)-1-(2-propyl-1H-inden-3-yl)naphthalene is as follows:

[0170] Add 2-propyl-1H-inden-3-yltrifluoromethanesulfonate (0.1 mmol, 30.6 mg), (2-(heptoxy)naphth-1-yl)boronic acid (0.2 mmol, 57.2 mg), [PdCl2·L6] (4.0 mg, 0.005 mmol, 5.0 mmol%), and potassium phosphate (K3PO4, 42.5 mg, 0.2 mmol) to a septum. Evacuate the system and purge with argon gas. Repeat this process three times. Then add toluene (0.8 mL) and water (0.2 mL), and stir the mixture at 25 °C for 48.0 hours. After the reaction was completed, the solvent was removed under vacuum, and the crude product was purified by column chromatography (eluting buffer was petroleum ether solution of 0.5% ethyl acetate) to give 28.4 mg (S)-2-(heptoxy)-1-(2-propyl-1H-inden-3-yl)naphthalene, with a yield of 95% and an enantiomeric excess of 90%.

[0171] Using nuclear magnetic resonance hydrogen spectroscopy (NMR) 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The product obtained in this embodiment was analyzed by C NMR.

[0172] 1 H NMR (500MHz, CDCl3) δ7.88(d,J=9.0Hz,1H),7.85(dd,J=8.0,1.5Hz,1H),7.57(dd,J=8.5,1.5Hz,1H),7.50(d d,J=6.5,1.5Hz,1H),7.38(d,J=9.0Hz,1H),7.37–7.29(m,2H),7.12(dtd,J=16.0,7.5,1.5Hz,2H),6.74–6.6 9(m,1H),4.02(dt,J=9.5,6.5Hz,1H),3.95(dt,J=9.5,6.5Hz,1H),3.65(d,J=22.5Hz,1H),3.58(d,J=22.5Hz ,1H),2.32–2.24(m,2H),1.60–1.48(m,5H),1.23–1.11(m,8H),0.86(t,J=7.0Hz,3H),0.80(t,J=7.5Hz,3H).

[0173] 13C NMR (126MHz, CDCl3) δ154.6,147.7,147.6,142.5,133.72,133.69,129.3,129.1,128.0,126.14,126.1 0,125.8,123.6,123.3,119.9,115.9,69.9,40.6,31.9,31.8,29.6,29.0,25.9,22.6,22.5,14.3,14.2.

[0174] 1H NMR spectrum 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 C NMR data confirm that the product obtained in this embodiment is (S)-2-(heptoxy)-1-(2-propyl-1H-indene-3-yl)naphthalene.

[0175] Example 13: Preparation of (S)-2-(cyclohexylmethoxy)-1-(2-propyl-1H-inden-3-yl)naphthalene

[0176] The synthetic route for (S)-2-(cyclohexylmethoxy)-1-(2-propyl-1H-inden-3-yl)naphthalene is as follows:

[0177]

[0178] The preparation method of (S)-2-(cyclohexylmethoxy)-1-(2-propyl-1H-inden-3-yl)naphthalene is as follows:

[0179] Add 2-propyl-1H-inden-3-yl trifluoromethanesulfonate (0.1 mmol, 30.6 mg), (2-(cyclohexylmethoxy)naphth-1-yl)boronic acid (0.2 mmol, 56.8 mg), [PdCl2·L6] (4.0 mg, 0.005 mmol, 5.0 mmol%), and potassium phosphate (K3PO4, 42.5 mg, 0.2 mmol) to a septum. Evacuate the system and purge with argon gas. Repeat this process three times. Then add toluene (0.8 mL) and water (0.2 mL), and stir the mixture at 25 °C for 48.0 hours. After the reaction was completed, the solvent was removed under vacuum, and the crude product was purified by column chromatography (elution buffer was petroleum ether solution of 0.5% ethyl acetate) to give 14.3 mg (S)-2-(cyclohexylmethoxy)-1-(2-propyl-1H-inden-3-yl)naphthalene, with a yield of 36% and an enantiomeric excess of 86%.

[0180] Using nuclear magnetic resonance hydrogen spectroscopy (NMR) 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The product obtained in this embodiment was analyzed by C NMR.

[0181] 1 H NMR(500MHz, CDCl3)δ7.86(d,J=9.0Hz,1H),7.85–7.81(m,1H),7.56(d,J=8.5Hz,1H),7 .48(s,1H),7.36(d,J=9.0Hz,1H),7.35–7.27(m,2H),7.10(tt,J=8.0,6.5Hz,2H),6.68 (dd,J=7.0,1.5Hz,1H),3.84–3.70(m,2H),3.63(d,J=22.5Hz,1H),3.54(d,J=22.5Hz,1 H),2.25(t,J=7.5Hz,2H),1.57–1.45(m,10H),1.13–0.98(m,3H),0.77(d,J=7.5Hz,3H). 13 C NMR (126MHz, CDCl3) δ154.7,147.6,147.6,142.5,133.8,133.7,129.3,129.1,128.0,126.1,126.1,125.8, 123.6,123.6,123.2,120.0,119.6,116.1,75.6,40.6,38.0,31.9,29.8,29.7,26.6,25.9,25.8,22.5,14.3.

[0182] 1H NMR spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 C NMR data confirm that the product obtained in this embodiment is (S)-2-(cyclohexylmethoxy)-1-(2-propyl-1H-indene-3-yl)naphthalene.

[0183] Example 14: Preparation of (S)-2-(cyclopentoxy)-1-(2-propyl-1H-inden-3-yl)naphthalene

[0184] The synthetic route for (S)-2-(cyclopentoxy)-1-(2-propyl-1H-inden-3-yl)naphthalene is as follows:

[0185]

[0186] The preparation method of (S)-2-(cyclopentoxy)-1-(2-propyl-1H-inden-3-yl)naphthalene is as follows:

[0187] Add 2-propyl-1H-inden-3-yltrifluoromethanesulfonate (0.1 mmol, 30.6 mg), (2-cyclopentoxynaphth-1-yl)boronic acid (0.2 mmol, 51.2 mg), [PdCl2·L6] (4.0 mg, 0.005 mmol, 5.0 mmol%), and potassium phosphate (K3PO4, 42.5 mg, 0.2 mmol) to a septum. Evacuate the system and purge with argon gas. Repeat this process three times. Then add toluene (0.8 mL) and water (0.2 mL), and stir the mixture at 25 °C for 48.0 hours. After the reaction was completed, the solvent was removed under vacuum, and the crude product was purified by column chromatography (eluting buffer was petroleum ether solution of 0.5% ethyl acetate) to obtain 28.4 mg (S)-2-(cyclopentoxy)-1-(2-propyl-1H-inden-3-yl)naphthalene, with a yield of 77% and an enantiomeric excess of 92%.

[0188] Using nuclear magnetic resonance hydrogen spectroscopy (NMR) 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The product obtained in this embodiment was analyzed by C NMR.

[0189] 1 H NMR(500MHz, CDCl3) δ7.87(d,J=9.0Hz,1H),7.85–7.81(m,1H),7.55(dd,J=8.5,1.5Hz,1H),7.49(dt,J =7.0,1.0Hz,1H),7.37(d,J=9.0Hz,1H),7.35–7.27(m,2H),7.17–7.04(m,2H),6.74–6.65(m,1H),4.87– 4.75(m,1H),3.63(d,J=22.5Hz,1H),3.56(d,J=22.5Hz,1H),2.26(td,J=7.5,1.5Hz,2H),1.74(tt,J=8. 0,4.0Hz,2H),1.64(td,J=8.0,4.5Hz,2H),1.60–1.44(m,4H),1.44–1.37(m,2H),0.80(t,J=7.5Hz,3H).

[0190] 13C NMR (126MHz, CDCl3) δ153.4,147.7,147.6,142.5,133.81,133.78,129.2,128.9,128.0,126.1,126.0, 125.8,123.6,123.5,123.2,120.2,120.0,117.0,80.9,40.5,33.2,32.8,31.9,23.9,23.7,22.5,14.3.

[0191] 1H NMR spectrum 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 C NMR data confirm that the product obtained in this embodiment is (S)-2-(cyclopentoxy)-1-(2-propyl-1H-indene-3-yl)naphthalene.

[0192] Example 15: Preparation of (S)-2-((4-methylbenzyl)oxy)-1-(2-propyl-1H-inden-3-yl)naphthalene

[0193] The synthetic route for (S)-2-((4-methylbenzyl)oxy)-1-(2-propyl-1H-inden-3-yl)naphthalene is as follows:

[0194]

[0195] The preparation method of (S)-2-((4-methylbenzyl)oxy)-1-(2-propyl-1H-inden-3-yl)naphthalene is as follows:

[0196] Add 2-propyl-1H-inden-3-yltrifluoromethanesulfonate (0.1 mmol, 30.6 mg), 2-((4-methylbenzyl)oxy)naphth-1-ylboronic acid (0.2 mmol, 58.4 mg), [PdCl2·L6] (4.0 mg, 0.005 mmol, 5.0 mmol%), and potassium phosphate (K3PO4, 42.5 mg, 0.2 mmol) to a septum. Evacuate the system and purge with argon gas. Repeat this process three times. Then add toluene (0.8 mL) and water (0.2 mL), and stir the mixture at 25 °C for 48.0 hours. After the reaction was completed, the solvent was removed under vacuum, and the crude product was purified by column chromatography (eluting buffer was petroleum ether solution of 0.5% ethyl acetate) to give 24.3 mg (S)-2-((4-methylbenzyl)oxy)-1-(2-propyl-1H-inden-3-yl)naphthalene, with a yield of 60% and an enantiomeric excess of 92%.

[0197] Using nuclear magnetic resonance hydrogen spectroscopy (NMR) 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The product obtained in this embodiment was analyzed by C NMR.

[0198] 1 H NMR(400MHz, CDCl3)δ7.88–7.81(m,2H),7.59(dq,J=8.0,1.0Hz,1H),7.54–7.48(m,1H) ,7.38(d,J=9.0Hz,1H),7.37–7.28(m,2H),7.14(pd,J=7.5,1.5Hz,2H),7.07–7.01(m,4 H),6.77–6.71(m,1H),5.08(d,J=12.5Hz,1H),5.04(d,J=12.5Hz,1H),3.64(s,1H),3.6 1(s,1H),2.30(s,3H),2.27(d,J=8.0Hz,2H),1.54–1.49(m,2H),0.78(t,J=7.5Hz,3H).

[0199] 13 C NMR (101MHz, CDCl3) δ154.2,148.0,147.5,142.6,137.2,134.7,133.7,133.6,129.5,129.1,129.1, 128.0,127.1,126.2,125.8,123.9,123.8,123.4,120.0,116.4,71.6,40.7,32.0,22.5,21.3,14.3.

[0200] 1H NMR spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 C NMR data confirm that the product obtained in this embodiment is (S)-2-((4-methylbenzyl)oxy)-1-(2-propyl-1H-indene-3-yl)naphthalene.

[0201] Example 16: Preparation of (S)-2-((4-(tert-butyl)benzyl)oxy)-1-(2-propyl-1H-inden-3-yl)naphthalene

[0202] The synthetic route for (S)-2-((4-(tert-butyl)benzyl)oxy)-1-(2-propyl-1H-inden-3-yl)naphthalene is as follows:

[0203]

[0204] The preparation method of (S)-2-((4-(tert-butyl)benzyl)oxy)-1-(2-propyl-1H-inden-3-yl)naphthalene is as follows:

[0205] Add 2-propyl-1H-inden-3-yl trifluoromethanesulfonate (0.1 mmol, 30.6 mg), (2-((4-(tert-butyl)benzyl)oxy)naphth-1-yl)boronic acid (0.2 mmol, 66.8 mg), [PdCl2·L6] (4.0 mg, 0.005 mmol, 5.0 mmol%), and potassium phosphate (K3PO4) to a 25 mL Shrek tube with a diaphragm. 44 42.5 mg (0.2 mmol) of toluene and argon gas were added to the mixture, and the mixture was evacuated and purged with argon gas. This process was repeated three times. Then, toluene (0.8 mL) and water (0.2 mL) were added, and the mixture was stirred at 25 °C for 48.0 hours. After the reaction was complete, the solvent was removed under vacuum, and the crude product was purified by column chromatography (eluent: 0.5% ethyl acetate in petroleum ether) to give 29.5 mg (S)-2-((4-(tert-butyl)benzyl)oxy)-1-(2-propyl-1H-inden-3-yl)naphthalene, in a yield of 66% and an enantiomeric excess of 95%.

[0206] Using nuclear magnetic resonance hydrogen spectroscopy (NMR) 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The product obtained in this embodiment was analyzed by C NMR.

[0207] 1 H NMR(400MHz, CDCl3)δ7.79–7.72(m,2H),7.49(ddd,J=8.0,1.5,1.0Hz,1H),7.45–7.40 (m,1H),7.31(d,J=9.0Hz,1H),7.28–7.19(m,2H),7.19–7.15(m,2H),7.10–6.98(m,4H ),6.68–6.61(m,1H),4.99(d,J=12.5Hz,1H),4.95(d,J=12.5Hz,1H),3.55(s,1H),3.5 3(s,1H),2.19(t,J=7.7Hz,2H),1.47–1.39(m,2H),1.20(s,9H),0.69(t,J=7.4Hz,3H).

[0208] 13 C NMR (101MHz, CDCl3) δ154.3,150.5,148.0,147.5,142.6,134.8,133.7,133.6,129.6,129.2,128.0,12 6.8,126.2,125.8,125.3,123.9,123.8,123.4,120.0,116.5,71.6,40.7,34.6,32.0,31.5,22.5,14.4.

[0209] 1H NMR spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 C NMR data confirm that the product obtained in this embodiment is (S)-2-((4-(tert-butyl)benzyl)oxy)-1-(2-propyl-1H-indene-3-yl)naphthalene.

[0210] Example 17: Preparation of (S)-2-((3,5-dimethylbenzyl)oxy)-1-(2-propyl-1H-inden-3-yl)naphthalene

[0211] The synthetic route for (S)-2-((3,5-dimethylbenzyl)oxy)-1-(2-propyl-1H-inden-3-yl)naphthalene is as follows:

[0212]

[0213] The preparation method of (S)-2-((3,5-dimethylbenzyl)oxy)-1-(2-propyl-1H-inden-3-yl)naphthalene is as follows:

[0214] Add 2-propyl-1H-inden-3-yltrifluoromethanesulfonate (0.1 mmol, 30.6 mg), 2-((3,5-dimethylbenzyl)oxy)naphth-1-ylboronic acid (0.2 mmol, 61.2 mg), [PdCl2·L6] (4.0 mg, 0.005 mmol, 5.0 mmol%), and potassium phosphate (K3PO4, 42.5 mg, 0.2 mmol) to a septum. Evacuate the system and purge with argon gas. Repeat this process three times. Then add toluene (0.8 mL) and water (0.2 mL), and stir the mixture at 25 °C for 48.0 hours. After the reaction was completed, the solvent was removed under vacuum, and the crude product was purified by column chromatography (elution buffer was petroleum ether solution of 0.5% ethyl acetate) to give 34.7 mg (S)-2-((3,5-dimethylbenzyl)oxy)-1-(2-propyl-1H-inden-3-yl)naphthalene, with a yield of 83% and an enantiomeric excess of 93%.

[0215] Using nuclear magnetic resonance hydrogen spectroscopy (NMR) 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The product obtained in this embodiment was analyzed by C NMR.

[0216] 1H NMR(400MHz, CDCl3)δ7.91–7.83(m,2H),7.63(dd,J=8.0,1.5Hz,1H),7.58–7.50(m,1H), 7.43–7.39(m,1H),7.39–7.30(m,2H),7.22–7.11(m,2H),6.85(s,1H),6.83–6.72(m,3H), 5.06(d,J=12.5Hz,1H),5.02(d,J=12.5Hz,1H),3.66(d,J=28.0Hz,1H),3.63(d,J=28.0Hz ,1H),2.30(td,J=8.0,2.0Hz,2H),2.21(s,6H),1.59–1.50(m,2H),0.80(t,J=7.5Hz,3H).

[0217] 13 C NMR (101MHz, CDCl3) δ154.2,148.0,147.5,142.6,137.9,137.7,133.7,129.5,129.2,129.1,128.1,126 .3,126.2,125.8,124.7,123.9,123.8,123.4,120.0,119.9,116.2,71.6,40.7,32.0,22.5,21.3,14.3.

[0218] 1H NMR spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 C NMR data confirm that the product obtained in this embodiment is (S)-2-((3,5-dimethylbenzyl)oxy)-1-(2-propyl-1H-indene-3-yl)naphthalene.

[0219] Example 18: Preparation of (S)-2-((3,5-di-tert-butylbenzyl)oxy)-1-(2-propyl-1H-inden-3-yl)naphthalene

[0220] The synthetic route for (S)-2-((3,5-di-tert-butylbenzyl)oxy)-1-(2-propyl-1H-inden-3-yl)naphthalene is as follows:

[0221]

[0222] The preparation method of (S)-2-((3,5-di-tert-butylbenzyl)oxy)-1-(2-propyl-1H-inden-3-yl)naphthalene is as follows:

[0223] Add 2-propyl-1H-inden-3-yl trifluoromethanesulfonate (0.1 mmol, 30.6 mg), (2-((3,5-di-tert-butylbenzyl)oxy)naphth-1-yl)boronic acid (0.2 mmol, 78.0 mg), [PdCl2·L6] (4.0 mg, 0.005 mmol, 5.0 mmol%), and potassium phosphate (K3PO4, 42.5 mg, 0.2 mmol) to a 25 mL Shrek tube with a diaphragm. Evacuate the system and purge with argon gas. Repeat this operation three times. Then add toluene (0.8 mL) and water (0.2 mL), and stir the mixture at 25 °C for 48.0 hours. After the reaction was completed, the solvent was removed under vacuum, and the crude product was purified by column chromatography (elution buffer was petroleum ether solution of 0.5% ethyl acetate) to give 40.2 mg (S)-2-((3,5-di-tert-butylbenzyl)oxy)-1-(2-propyl-1H-inden-3-yl)naphthalene, with a yield of 80% and an enantiomeric excess of 94%.

[0224] Using nuclear magnetic resonance hydrogen spectroscopy (NMR) 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The product obtained in this embodiment was analyzed by C NMR.

[0225] 1 H NMR(400MHz, CDCl3)δ7.89(d,J=8.8Hz,1H),7.87–7.83(m,1H),7.62–7.58(m,1H),7.51–7.47(m,1 H),7.45(d,J=9.2Hz,1H),7.38–7.29(m,2H),7.27(t,J=2.0Hz,1H),7.16–7.07(m,2H),7.04(d,J= 2.0Hz,2H),6.81–6.75(m,1H),5.10(d,J=12.0Hz,1H),5.06(d,J=12.0Hz,1H),3.64(s,1H),3.62( s,1H),2.29(ddd,J=8.0,6.8,4.0Hz,2H),1.54–1.46(m,2H),1.22(s,18H),0.76(t,J=7.2Hz,3H).

[0226] 13C NMR (101MHz, CDCl3) δ154.4,150.8,147.8,147.5,142.5,136.7,133.8,133.7,129.5,129.2,128.1,12 6.3,126.2,125.8,123.8,123.5,121.4,121.1,119.9,116.2,72.2,40.7,34.9,31.9,31.5,22.6,14.3.

[0227] 1H NMR spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 C NMR data confirm that the product obtained in this embodiment is (S)-2-((3,5-di-tert-butylbenzyl)oxy)-1-(2-propyl-1H-indene-3-yl)naphthalene.

[0228] Example 19: Preparation of (S)-2-(naphth-1-ylmethoxy)-1-(2-propyl-1H-inden-3-yl)naphthalene

[0229] The synthetic route for (S)-2-(naphth-1-ylmethoxy)-1-(2-propyl-1H-inden-3-yl)naphthalene is as follows:

[0230]

[0231] The preparation method of (S)-2-(naphth-1-ylmethoxy)-1-(2-propyl-1H-inden-3-yl)naphthalene is as follows:

[0232] Add 2-propyl-1H-inden-3-yl trifluoromethanesulfonate (0.1 mmol, 30.6 mg), (2-(naphthyl-1-ylmethoxy)naphthyl-1-yl)boronic acid (0.2 mmol, 65.6 mg), [PdCl2·L6] (4.0 mg, 0.005 mmol, 5.0 mmol%), and potassium phosphate (K3PO4, 42.5 mg, 0.2 mmol) to a septum. Evacuate the system and purge with argon gas. Repeat this process three times. Then add toluene (0.8 mL) and water (0.2 mL), and stir the mixture at 25 °C for 48.0 hours. After the reaction was completed, the solvent was removed under vacuum, and the crude product was purified by column chromatography (eluting buffer was petroleum ether solution of 0.5% ethyl acetate) to give 42.7 mg (S)-2-(naphth-1-ylmethoxy)-1-(2-propyl-1H-inden-3-yl)naphthalene, with a yield of 97% and an enantiomeric excess of 95%.

[0233] Using nuclear magnetic resonance hydrogen spectroscopy (NMR) 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 The product obtained in this embodiment was analyzed by C NMR.

[0234] 1 H NMR(500MHz, CDCl3)δ7.91–7.86(m,2H),7.78(td,J=6.5,2.5Hz,2H),7.72(d,J=8.5Hz ,1H),7.64–7.58(m,2H),7.51(t,J=3.5Hz,2H),7.46–7.43(m,2H),7.40–7.35(m,2H), 7.30(dd,J=8.5,1.5Hz,1H),7.22–7.10(m,2H),6.87–6.82(m,1H),5.30–5.22(m,2H), 3.66(s,1H),3.63(s,1H),2.37–2.25(m,2H),1.54–1.48(m,2H),0.78(t,J=7.5Hz,3H).

[0235] 13 C NMR (126MHz, CDCl3) δ154.1,148.1,147.5,142.6,135.2,133.7,133.3,132.9,129.6,129.2,128.6,128.0,127.9,127.8,127.0,12 6.5,126.5–126.2(m),126.1,125.9,125.8,125.5,124.9,123.9,123.4,120.0,119.2,116.2,107.4,71.7,40.7,32.0,22.5,14.3.

[0236] 1H NMR spectrum ( 1 H NMR) and carbon nuclear magnetic resonance (NMR) 13 C NMR data confirm that the product obtained in this embodiment is (S)-2-(naphth-1-ylmethoxy)-1-(2-propyl-1H-indene-3-yl)naphthalene.

[0237] Example 20

[0238] The preparation method was basically the same as in Example 1, except that [PdCl2·L6] (4.0 mg, 0.005 mmol, 5.0 mmol%) was replaced with [PdCl2·L2] (3.2 mg, 0.005 mmol, 5.0 mmol%); the yield of the obtained product was 86%, and the enantiomeric excess was 35%.

[0239] The structural formula of ligand L2 is as follows:

[0240]

[0241] Comparative Example 1

[0242] The preparation method is basically the same as that in Example 1, except that: in this comparative example, compound 2 is 2-[2-(benzyloxy)-1-naphthyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborhecyclopentane, the yield of the product is 55%, and the enantiomeric excess is 65%.

[0243] Comparative Example 2

[0244] The preparation method is basically the same as that in Example 1, except that: in this comparative example, compound 1 is 3-bromo-2-propyl-1H-indene, and the yield of the obtained product is 15%.

[0245] Comparative Example 3

[0246] The preparation method is basically the same as in Example 1, except that: in this comparative example, compound 1 is 3-chloro-2-propyl-1H-indene, and the yield of the obtained product is <5%.

[0247] Comparative Example 4

[0248] The preparation method was basically the same as in Example 1, except that the amount of [PdCl2·L6] added was 2 mg, the yield of the product was 45%, and the enantiomeric excess value was 95%.

[0249] Comparing Example 1 with Comparative Examples 1-4, it can be seen that when the amount of reactant or catalyst is outside the range of the present invention, the yield of the product decreases significantly, indicating that the method of the present invention can efficiently prepare axially chiral indene ligands.

[0250] The above description is merely a preferred embodiment of the present invention, and the present invention is not limited to the above embodiments. It is understood that other improvements and variations that are directly derived or conceived by those skilled in the art without departing from the spirit and concept of the present invention should be considered to be included within the protection scope of the present invention.

Claims

1. A class of axially chiral indenyl ligands, characterized in that, The general structural formula of the axially chiral indenyl ligand is shown in Formula 3: In the formula, R1 includes at least one of cyclohexyl, isopropyl, heptyl, cyclohexylmethyl, 2-cyclopentyl, naphthyl, naphth-2-ylmethyl, substituted or unsubstituted benzyl; The substituents on the substituted benzyl group include at least one of methyl and tert-butyl groups; The R2 includes at least one of hydrogen atom, methyl, phenyl, isopropyl, tert-butyl, amino, epoxypentane, halogen, trifluoromethyl, and trifluoromethoxy. The R3 includes at least one of n-propyl, methyl, benzyl, ethyl, butyl, n-hexyl, cyclohexylmethyl, 4-methylbenzyl, 4-methoxybenzyl, 3,4,5-trimethoxybenzyl, adamantyl, methoxymethyl ether, isopropyl, naphthylmethyl, substituted or unsubstituted phenyl; The substituents on the substituted phenyl group include at least one of methyl, tert-butyl, and halogen; The R4 includes at least one of hydrogen atom, methoxy group, n-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, and p-methoxyphenyl group.

2. A method for preparing the axially chiral indenyl ligand according to claim 1, characterized in that, Includes the following steps: The axially chiral indene ligand was prepared by an asymmetric Suzuki-Miyaura cross-coupling reaction in the presence of chiral ligands and a metal catalyst, using compounds 1 and 2 as raw materials, under alkaline conditions and in a solvent. The general structural formula of compound 1 is shown in Formula 1: In the formula, R3 includes at least one of n-propyl, methyl, benzyl, ethyl, butyl, n-hexyl, cyclohexylmethyl, 4-methylbenzyl, 4-methoxybenzyl, 3,4,5-trimethoxybenzyl, adamantyl, methoxymethyl ether, isopropyl, naphthylmethyl, substituted or unsubstituted phenyl. The substituents on the substituted phenyl group include at least one of methyl, tert-butyl, and halogen; The R4 includes at least one of hydrogen atom, methoxy group, n-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, and p-methoxyphenyl group; The general structural formula of compound 2 is shown in Formula 2: In the formula, R1 includes at least one of cyclohexyl, isopropyl, heptyl, cyclohexylmethyl, 2-cyclopentyl, naphthyl, naphth-2-ylmethyl, substituted or unsubstituted benzyl; The substituents on the substituted benzyl group include at least one of methyl and tert-butyl groups; The R2 includes at least one of hydrogen atom, methyl, phenyl, isopropyl, tert-butyl, amino, epoxypentane, halogen, trifluoromethyl, and trifluoromethoxy.

3. The preparation method according to claim 2, characterized in that, The specific steps include: mixing compound 1, compound 2, metal catalyst, chiral ligand, base, and solvent, reacting under a protective atmosphere, and then obtaining the axially chiral indene ligand through post-treatment.

4. The preparation method according to claim 2 or 3, characterized in that, The chiral ligands include at least one of (11bR)-N,N-dimethyldinaphthalo[2,1-d:1',2'-f][1,3,2]dioxaphosphatane-4-amine, (R)-(2'-methoxy-[1,1'-binaphthyl]-2-yl)diphenylphosphine, (R)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, (R)-5,5'-bis(diphenylphosphino)-4,4'-bibenzo[d][1,3]dioxacyclopentene, (6,6'-dimethoxy-[1,1'-biphenyl]-2,2'-diyl)bis(diphenylphosphine), and (5,5'-dichloro-6,6'-dimethoxy-[1,1'-biphenyl]-2,2'-diyl)bis(diphenylphosphine); And / or, the metal catalyst includes a divalent palladium catalyst.

5. The preparation method according to claim 4, characterized in that, The divalent palladium catalyst includes at least one of palladium acetate, palladium chloride, palladium sulfate, palladium nitrate, dichlorobis(triphenylphosphine) palladium, dichlorobis(diphenylphosphinemethane) palladium, dichlorobis(pyridine) palladium, and palladium dibromide; And / or, the metal catalyst forms a complex with the chiral ligand, preferably, the complex comprising a complex of palladium chloride and (5,5'-dichloro-6,6'-dimethoxy-[1,1'-biphenyl]-2,2'-diyl)bis(diphenylphosphine).

6. The preparation method according to claim 3, characterized in that, The alkali includes at least one of potassium carbonate, potassium phosphate, cesium carbonate, lithium tert-butoxide, and cesium neopentanoate; And / or, the solvent includes at least one of dichloromethane, ethyl acetate, trifluorotoluene, fluorobenzene, 1,4-dioxane, toluene, tetrahydrofuran, 2-methyltetrahydrofuran, and water; Preferably, the solvent comprises a mixture of toluene and water; wherein the volume ratio of toluene to water in the mixture is (1-10):

1.

7. The preparation method according to claim 2 or 3, characterized in that, The molar ratio of the metal catalyst, chiral ligand, compound 1, and compound 2 is 0.05:(0.05~0.15):(1~2):(1~2).

8. The preparation method according to claim 3, characterized in that, The molar ratio of the base to compound 1 is (1-4):(1-4).

9. The preparation method according to claim 3, characterized in that, The reaction temperature is 0–140°C, and the time is 24–48 h; And / or, the protective atmosphere includes at least one of nitrogen, argon, and helium.

10. The application of a class of axially chiral indenyl ligands in the field of catalysis, characterized in that, The axially chiral indene ligand is the axially chiral indene ligand of claim 1, and / or the axially chiral indene ligand prepared by the preparation method of any one of claims 2-9.

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