CN106279292B

CN106279292B - Metal iridium complex, monocrystalline, benzindole class compound and synthetic method and application

Info

Publication number: CN106279292B
Application number: CN201510305993.8A
Authority: CN
Inventors: 游书力; 叶克印; 吴可嘉
Original assignee: Shanghai Institute of Organic Chemistry of CAS
Current assignee: Shanghai Institute of Organic Chemistry of CAS
Priority date: 2015-06-04
Filing date: 2015-06-04
Publication date: 2018-12-18
Anticipated expiration: 2035-06-04
Also published as: CN106279292A

Abstract

The invention discloses a kind of metal iridium complex, monocrystalline, benzindole class compound and synthetic method and applications.This method comprises the steps of in organic solvent, in the presence of base, by chiral triazole Cabbeen salt respectively with [Ir (cod) X¹]₂、[Ir(cod)X^1a]₂、[Ir(cod)X^1b]₂、[Ir(cod)X^1c]₂、[Ir(cod)X^1d]₂Or [Ir (cod) X^1e]₂Carry out complex reaction.Application the invention also discloses metal iridium complex as catalyst in asymmetric allylic substitution.For metal iridium complex of the invention using triazole Cabbeen as ligand, synthetic method and post-processing are simple, and have extraordinary effect in the asymmetric allylic substitution of metal iridium catalysis.

Description

Metal iridium complex, single crystal, benzo indole compound, synthesis method and application

Technical Field

The invention relates to a metal iridium complex, a single crystal, a benzindole compound, a synthetic method and application.

Background

The asymmetric allyl substitution reaction catalyzed by the iridium metal can construct carbon-carbon bonds and carbon-hybrid bonds with high enantioselectivity and regioselectivity, and is widely applied to synthesis. The catalysts used in the reactions are mainly[Ir(cod)Cl]₂And chiral phosphine nitrogen ligands [ (a) Miyabe, h.; Takemoto, y.synlett2005,1641.(b) Takeuchi, r.; Kezuka, s.synthes 2006,3349.(c) Helmchen, g.; Dahnz, a.; D ü bon, p.; Schelwies, m.; Weihofen, r.chem.commun.2007,675.(D) Helmchen chen, g.; Iridium compounds In organic Synthesis; 2, l.a.; lever, c.eds.; wil VCH: Weinheim, german, 2009; p211.(e) Hartwig, f.; stanly, l.m.chem.s.r., usa, 2011, r.7, p.g., Hartwig, r.f.;, chen, l.m.r.26, r.7. org, p.g.;, r. t. p. t. g.; r.p.g. 7, r.g., r.7. org, r.p.g.]. The N-heterocyclic carbene can be used as a good metal ligand to be applied to catalytic reaction as same as a phosphine ligand due to the strong sigma electron-donating capability and the unique spatial structure of the N-heterocyclic carbene. Compared with common imidazole carbene, imidazoline carbene and thiazole carbene, the triazole carbene has less application in metal catalysis due to the weak electron donating capability. In particular, the use of chiral triazole carbenes as ligands in allyl substitution reactions has not been reported in the literature to date.

Disclosure of Invention

The invention aims to provide a metal iridium complex, a single crystal and a benzo indole compound which are completely different from the prior art, a synthetic method and application thereof. The metal iridium complex takes triazole carbene as a ligand, has simple synthesis method and post-treatment, and has good effect in the allyl substitution reaction catalyzed by metal iridium. Therefore, the metal iridium complex has very important significance for the expansion of the type of the metal iridium-catalyzed allyl substitution reaction catalyst and the abundance of the reaction types, and a class of benzindole compounds is prepared in the metal iridium-catalyzed allyl substitution reaction.

The invention provides a metal iridium complex shown in a general formula I, a general formula II, a general formula III, a general formula IV, a general formula V or a general formula VI, wherein carbon marked by x is chiral carbon or non-chiral carbon, and when the carbon is chiral carbon, the chiral carbon is in an S configuration or an R configuration;

in the general formulae I to VI, R¹、R^1a、R^1b、R^1c、R^1dAnd R^1eIndependently is C₁-C₈Alkyl of (C)₃-C₆Cycloalkyl of, C₁-C₈Perfluoroalkyl group of (1), substituted or unsubstituted C₆-C₂₀Or substituted or unsubstituted C₂-C₂₀The heteroaryl group of (a);

R²、R^2’、R^2a、R^2a’、R^2b、R^2b’、R^2cand R^2c’Independently of one another is hydrogen, C₁-C₈Alkyl of (C)₃-C₆Cycloalkyl of, C₁-C₈Perfluoroalkyl group of (1), substituted or unsubstituted C₆-C₂₀Or substituted or unsubstituted C₂-C₂₀The heteroaryl group of (a); or R²And R^2’And the carbon atoms to which they are attached together form C₅-C₈Cycloalkyl groups of (a);

R³is composed ofWherein R is_aIs C₁-C₈Alkyl of (C)₁-C₈Perfluoroalkyl group of (1), substituted or unsubstituted C₆-C₂₀Or substituted or unsubstituted C₂-C₂₀The heteroaryl group of (a); r_bIs C₁-C₈Alkyl of (C)₁-C₈Alkoxy group of (C)₁-C₈Perfluoroalkyl group of (1), substituted or unsubstituted C₆-C₂₀Aryl of (2), or substituted or unsubstituted C₂-C₂₀The heteroaryl group of (a);

R⁴、R^4aand R^4bIndependently of one another is hydrogen, C₁-C₈Alkyl orWherein R is_c、R_c' and R_c"independently is C₁-C₈Alkyl groups of (a);

R⁵is hydrogen, halogen, C₁-C₈Alkyl of (C)₃-C₆Cycloalkyl of, C₁-C₈Perfluoroalkyl group of (1), substituted or unsubstituted C₆-C₂₀Or substituted or unsubstituted C₆-C₂₀The heteroaryl group of (a);

X¹、X^1a、X^1b、X^1c、X^1dand X^1eIndependently is halogen or C₁-C₈Alkoxy group of (a);

wherein, said substituted C₆-C₂₀Aryl of (a) or said substituted C₂-C₂₀Said substitution in heteroaryl means substitution with one or more of the following substituents: halogen (the halogen is preferably F, Cl, Br or I), C₁-C₁₆Hydrocarbyloxy group of (said C)₁-C₁₆The hydrocarbyloxy group of (A) is preferably C₁-C₈Hydrocarbyloxy groups of (a); said C₁-C₈The hydrocarbyloxy group of (A) is preferably C₁-C₄Hydrocarbyloxy groups of (a); said C₁-C₄The hydrocarbyloxy group of (A) is preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy), C₁-C₁₆Alkyl (said C)₁-C₁₆The alkyl group of (A) is preferably C₁-C₈Alkyl groups of (a); said C₁-C₈The alkyl group of (A) is preferably C₁-C₄Alkyl groups of (a); said C₁-C₄The alkyl group of (A) is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl), C₁-C₁₆Fluoroalkyl (meth)C is₁-C₁₆By fluoroalkyl is meant C substituted by one or more fluorine atoms₁-C₁₆Alkyl groups of (a); said C₁-C₁₆The fluoroalkyl group of (A) is preferably C₁-C₈A fluoroalkyl group of (a); said C₁-C₈The fluoroalkyl group of (A) is preferably C₁-C₄A fluoroalkyl group of (a); said C₁-C₄The fluoroalkyl group of (a) is preferably a trifluoromethyl group), a nitro group or an amino group, and when the substituent is plural, the substituents are the same or different.

R¹、R^1a、R^1b、R^1c、R^1d、R^1e、R²、R²’、R^2a、R^2a’、R^2b、R^2b’、R^2c、R^2c’、R_a、R_b、R⁴、R^4a、R^4b、R_c、R_c’、R_c"and R⁵In (b), the C₁-C₈The alkyl group of (A) is preferably C₁-C₄Alkyl of (a), said C₁-C₄The alkyl group of (a) is preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group or a tert-butyl group.

R¹、R^1a、R^1b、R^1c、R^1d、R^1e、R²、R²’、R^2a、R^2a’、R^2b、R^2b’、R^2c、R^2c’And R⁵In (b), the C₃-C₆The cycloalkyl group of (b) is preferably cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

R¹、、R^1a、R^1b、R^1c、R^1d、R^1e、R²、R²’、R^2a、R^2a’、R^2b、R^2b’、R^2c、R^2c’、R_a、R_bAnd R⁵In (b), the C₁-C₈Is preferably perfluoroalkylIs composed of Wherein, including the respective isomeric forms.

R¹、R^1a、R^1b、R^1c、R^1d、R^1e、R²、R²’、R^2a、R^2a’、R^2b、R^2b’、R^2c、R^2c’、R_a、R_bAnd R⁵Wherein said substituted or unsubstituted C₆-C₂₀Aryl of (A) is preferably substituted or unsubstituted C₆-C₁₄Aryl group of (1). Said substituted or unsubstituted C₆-C₁₄The aryl group of (A) is preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted 9-anthracenyl groupOr substituted or unsubstituted 9-phenanthrylSaid substituted phenyl is preferably

R¹、R^1a、R^1b、R^1c、R^1d、R^1e、R²、R²’、R^2a、R^2a’、R^2b、R^2b’、R^2c、R^2c’、R_a、R_bAnd R⁵Wherein said substituted or unsubstituted C₂-C₂₀The heteroaryl group of (A) preferably means a substituted or unsubstituted C having O, N or S as a heteroatom and 1 to 4 heteroatoms₂-C₂₀The heteroaryl group of (a). The heteroatom is O, N or S, and the heteroatom number is 1-4 substituted or unsubstituted C₂-C₂₀The heteroaryl group of (A) is preferably substituted or unsubstituted C₂-C₁₀The heteroaryl group of (a). Said substituted or unsubstituted C₂-C₁₀The heteroaryl group of (a) is preferably a substituted or unsubstituted furyl group, a substituted or unsubstituted pyridyl group, or a substituted or unsubstituted thienyl group.

R_b、X¹、X^1a、X^1b、X^1c、X^1dAnd X^1eIn (b), the C₁-C₈Alkoxy of (3) is preferably C₁-C₄Alkoxy group of (2). Said C₁-C₄The alkoxy group of (b) is preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy.

X¹、X^1a、X^1b、X^1c、X^1dAnd X^1eThe halogen is preferably fluorine, chlorine, bromine or iodine.

When R is²And R^2’And the carbon atoms to which they are attached together form C₅-C₈In the case of a cycloalkyl group of (A), said C₅-C₈The cycloalkyl group of (b) is preferably cyclopentyl or cyclohexyl.

R³In (1), thePreferably is

R⁴、R^4aOr R^4bIn (1), thePreferably is

Preferably, the first and second liquid crystal films are made of a polymer,

in the general formula I, R¹Is C₃-C₆Cycloalkyl or substituted or unsubstituted C₆-C₂₀Aryl of (a); x¹Is halogen or C₁-C₈Alkoxy group of (2). In the general formula IThe structures may also contain chiral centres, e.g.

In the general formula II, R^1aIs C₃-C₆Cycloalkyl or substituted or unsubstituted C₆-C₂₀Aryl of (a); r²And R^2’Independently is substituted or unsubstituted C₆-C₂₀Or substituted or unsubstituted C₂-C₂₀The heteroaryl group of (a); or R²And R^2’And the carbon atoms to which they are attached together form C₅-C₈Cycloalkyl groups of (a); r³Is composed ofWherein R is_aIs C₁-C₈Alkyl of (C)₁-C₈Perfluoroalkyl group of (1), substituted or unsubstituted C₆-C₂₀Aryl of (2), or substituted or unsubstituted C₂-C₂₀The heteroaryl group of (a); r_bIs C₁-C₈Alkyl of (C)₁-C₈Alkoxy group of (C)₁-C₈Perfluoroalkyl group of (1), substituted or unsubstituted C₆-C₂₀Aryl of (2), or substituted or unsubstituted C₂-C₂₀The heteroaryl group of (a); x^1aIs halogen or C₁-C₈Alkoxy group of (a);

in the general formula III, R^1bIs substituted or unsubstituted C₆-C₂₀Aryl of (a); r^2a、R^2a’And R⁴Independently is C₁-C₈Alkyl groups of (a); x^1bIs halogen;

in the general formula IV, R^1cIs substituted or unsubstituted C₆-C₂₀Aryl of (a); r^2bAnd R^2b’Independently is C₁-C₈Alkyl of (C)₁-C₈Perfluoroalkyl group of (1), substituted or unsubstituted C₆-C₂₀Or substituted or unsubstituted C₂-C₂₀The heteroaryl group of (a); r^4aIndependently of one another is hydrogen, C₁-C₈Alkyl orWherein R is_c、R_c' or R_c"independently is C₁-C₈Alkyl groups of (a); r⁵Is hydrogen or halogen; x^1cIs halogen or C₁-C₈Alkoxy group of (a);

in the general formula V, R^1dIs substituted or unsubstituted C₆-C₂₀Aryl of (a); r^2c、R^2c’And R^4bIndependently of one another is hydrogen, C₁-C₈Alkyl of (C)₁-C₈Perfluoroalkyl group of (1), substituted or unsubstituted C₆-C₂₀Or substituted or unsubstituted C₂-C₂₀The heteroaryl group of (a); x^1cIs halogen or C₁-C₈Alkoxy group of (a);

in the general formula VI, R^1eIs substituted or unsubstituted C₆-C₂₀Aryl of (a); x^1eIs halogen or C₁-C₈Alkoxy group of (2).

The compound shown in the general formula I is preferably any one of the following compounds:

the compound represented by the formula II is preferably any one of the following compounds:

the compound represented by the formula III is preferably any one of the following compounds:

the compound represented by the formula IV is preferably any one of the following compounds:

the compound represented by the formula V is preferably any one of the following compounds:

the compound represented by formula VI is preferably any of the following compounds:

the invention also provides a single crystal of the metal iridium complex IIIa, which belongs to a monoclinic system in a single crystal X-ray diffraction spectrum using a radiation source Cu-K α, has a space group of P21, and has the following unit cell parameters: α -90 °, β -92.5300 (10 °), γ -90 °, unit cell volumeThe number of asymmetric units in the unit cell, Z, is 2;

the invention also provides a preparation method of the single crystal of the metal-iridium complex IIIa, which comprises the following steps: and (3) mixing the metal iridium complex IIIa and a benign solvent, then dropwise adding the poor solvent until turbidity just appears, dropwise adding the benign solvent, and standing.

The benign solvent is preferably a solvent having good solubility for the metal complex IIIa (solubility greater than 0.1mg/10mL at room temperature under 1 atm), and preferably a halogenated hydrocarbon solvent. The halogenated hydrocarbon solvent is preferably Dichloromethane (DCM). The amount of the benign solvent to be used is not particularly limited as long as the metal complex IIIa can be dissolved to give a clear and transparent solution. In general, the ratio of the benign solvent to the metal complex IIIa is preferably from 1mL/20mg to 1mL/40mg by volume.

The poor solvent is preferably a solvent having poor solubility (solubility of less than 0.1mg/100mL at room temperature under 1 standard atmosphere) for the metal-containing complex IIIa, and is preferably an alkane solvent. The alkane solvent is preferably n-hexane. The amount of the poor solvent is not particularly limited, and is generally such that the poor solvent is added dropwise to a solution of the iridium complex IIIa and the benign solvent just before clouding occurs. The volume and mass ratio of the poor solvent to the metal iridium complex IIIa is preferably 1mL/5mg-1mL/1 mg.

The mixing temperature may be a temperature conventional in the art, and is preferably 10 to 30 ℃. The temperature of said standing may be a temperature conventional in the art, preferably from-30 ℃ to-50 ℃.

The invention also provides a preparation method of the metal iridium complex shown in the general formula I, the general formula II, the general formula III, the general formula IV, the general formula V or the general formula VI, which comprises the following steps: in an organic solvent, in the presence of alkali, a compound shown as a formula a and [ Ir (cod) X¹]₂A compound represented by the formula b and [ Ir (cod) X^1a]₂A compound represented by the formula c and [ Ir (cod) X^1b]₂A compound represented by the formula d and [ Ir (cod) X^1c]₂A compound represented by the formula e and [ Ir (cod) X^1d]₂Or a compound of formula f with [ Ir (cod) X^1e]₂Carrying out a complexation reaction as shown below; respectively preparing metal iridium complexes shown in a general formula I, a general formula II, a general formula III, a general formula IV, a general formula V or a general formula VI;

wherein, the symbols, the radicalsThe definitions are all as described above; y is halogen, CF₃SO₃、OTf、BF₄Or ClO₄。

In Y, the halogen is preferably fluorine, chlorine, bromine or iodine. [ Ir (cod) X¹]₂～[Ir(cod)X^1e]₂In the above formula, cod means 1, 5-cyclooctadiene.

The methods and conditions of the complexation reaction may be those conventional in the art. The following methods are preferred in the present invention: the organic solvent is preferably one or more of aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, ether solvents, amide solvents, alkane solvents and nitrile solvents, and more preferably ether solvents. The aromatic hydrocarbon solvent is preferably one or more of benzene, toluene and xylene. The halogenated hydrocarbon solvent is preferably carbon tetrachloride (CCl)₄) Dichloromethane (DCM) and trichloromethane (CHCl)₃) One or more of (a). The ethereal solvent is preferably one or more of Tetrahydrofuran (THF), diethyl ether and 1, 4-dioxane, more preferably tetrahydrofuran. The amide solvent is preferably N, N-Dimethylformamide (DMF). The alkane solvent is preferably one or more of cyclohexane, n-pentane, n-hexane and n-heptane. The nitrile solvent is preferably acetonitrile. The base may be any base conventional in the art, preferably an inorganic base and/or an organic base. The inorganic base may be an inorganic base conventional in this kind of reaction in the art, and preferably is one or more of sodium carbonate, potassium carbonate, cesium carbonate, potassium phosphate, sodium hydride, sodium methoxide, sodium ethoxide, sodium acetate, potassium tert-butoxide, sodium tert-butoxide, and lithium tert-butoxide. The organic base may be an organic base conventional in the art for such reactions, preferably one or more of triethylamine, piperidine, pyridine, N-lutidine and 2, 6-lutidine. The [ Ir (cod) X¹]₂And a compound shown as a formula [ Ir (cod) X^1a]₂And a compound represented by the formula b, [ Ir (cod) X^1b]₂And a compound represented by the formula c, [ Ir (cod) X^1c]₂And a compound represented by the formula d, [ Ir (cod) X^1d]₂And a compound represented by the formula e or [ Ir (cod) X^1e]₂The molar ratio to the compound represented by the formula f is preferably 1:1 to 1:3.5, more preferably 1:2 to 1: 3.5. The [ Ir (cod) X¹]₂、[Ir(cod)X^1a]₂、[Ir(cod)X^1b]₂、[Ir(cod)X^1c]₂、[Ir(cod)X^1d]₂Or [ Ir (cod) X^1e]₂The molar ratio to the base is preferably from 1:1 to 1:20, more preferably from 2:15 to 1: 20. The organic solvent is mixed with [ Ir (cod) X¹]₂、[Ir(cod)X^1a]₂、[Ir(cod)X^1b]₂、[Ir(cod)X^1c]₂、[Ir(cod)X^1d]₂Or [ Ir (cod) X^1e]₂The volume/mass ratio of (B) is preferably 0.1mL/mg to 1 mL/mg. The reaction temperature is preferably from 0 ℃ to 150 ℃, more preferably from 25 ℃ to 125 ℃. The time for the complexing reaction is preferably 20 to 48 hours.

After the reaction is finished, the method can also comprise the operation of post-treatment. The post-treatment method can be a conventional method for post-treatment in the field, and preferably comprises the steps of removing the solvent from the reaction solution after the reaction is finished, and separating and purifying the crude product by recrystallization, thin-layer chromatography or column chromatography. The recrystallization solvent, the thin-layer chromatography developer, or the eluent for column chromatography is preferably a mixture of a polar solvent and a nonpolar solvent. The polar solvent is preferably an alcohol solvent and/or an ester solvent. The alcohol solvent is preferably one or more of methanol, ethanol and isopropanol. The ester solvent is preferably ethyl acetate. The nonpolar solvent is preferably a chlorinated hydrocarbon solvent and/or an alkane solvent. The chlorinated hydrocarbon solvent is preferably dichloromethane. The alkane solvent is preferably petroleum ether and/or n-hexane. The solvent for recrystallization is preferably one or more of dichloromethane-n-hexane, isopropanol-petroleum ether, ethyl acetate-n-hexane, and isopropanol-ethyl acetate-petroleum ether. The developing solvent for thin layer chromatography or the eluent for column chromatography is preferably one or more of isopropanol-petroleum ether, isopropanol-dichloromethane, methanol-dichloromethane, ethyl acetate-petroleum ether, ethyl acetate-n-hexane, and isopropanol-ethyl acetate-petroleum ether. In the recrystallization solvent, the thin-layer chromatography developer, or the eluent of column chromatography, the volume ratio of the polar solvent to the nonpolar solvent is preferably 1:1 to 1: 500. For example: ethyl acetate: petroleum ether ═ 1:1 to 1:500, and isopropanol: petroleum ether is 1:1 to 1: 500.

The invention also provides application of the metal iridium complex shown in the general formula I, the general formula II, the general formula III, the general formula IV, the general formula V or the general formula VI as a catalyst in asymmetric allyl substitution reaction.

The asymmetric allylic substitution reaction preferably comprises the steps of: in an organic solvent, under the action of alkali, and under the catalysis of one or more of the metal iridium complexes shown in the general formula I, the general formula II, the general formula III, the general formula IV, the general formula V or the general formula VI, carrying out asymmetric allyl substitution reaction shown in the following formula S1 on the compound shown in the formula S1 to obtain a benzindole compound shown in the formula P; wherein, the carbon marked by the letter is chiral carbon or non-chiral carbon, and when the carbon is chiral carbon, the chiral carbon is in S configuration or R configuration;

in the compound shown as the formula S1 and the compound shown as the formula P, R_a1Is mono-or polysubstituted, the same or different, selected from one or more of the following substituents: halogen, substituted or unsubstituted C₁-C₄Or substituted or unsubstituted C₁-C₄Alkoxy group of (a); r_b1Is substituted or unsubstituted C₁-C₄Or substituted or unsubstituted C₂-C₄Alkenyl of (a); r_c1Is composed ofWherein M is O or NH; r_d1Is C₁-C₄Alkyl, C substituted by one or more halogens₁-C₄Alkyl or C₁-C₄Alkoxy group of (a); r_e1Is C₁-C₄Alkyl or C₆-C₂₀An aryl group; r_a1And R_b1In (b), said substituted C₁-C₄Alkyl of (2) or said substituted C₁-C₄The substituent in the alkoxy group of (a) means a substituent substituted with one or more of the following substituents: halogen (the halogen is F, Cl, Br or I), C₁-C₄Alkoxy of (said C)₁-C₄The alkoxy group of (B) is preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy), C₁-C₄Alkyl (said C)₁-C₄The alkyl group of (A) is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl), C₆～C₂₀Aryl (said C)₆～C₂₀Aryl is preferably phenyl, or substituted by one or more C₁-C₄Alkoxy-substituted C₆-C₂₀Aryl, when there are more than one substituent, said substituents may be the same or different (said being substituted by one or more C's)₁-C₄Alkoxy-substituted C₆-C₂₀Aryl is preferably p-methoxyphenyl), and when the substituent is plural, the substituents may be the same or different.

R_a1In (3), the halogen is preferably F, Cl, Br or I.

R_a1Or R_b1Wherein said substituted or unsubstituted C₁-C₄The alkyl group of (a) is preferably a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted n-propyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted n-butyl group, a substituted or unsubstituted isobutyl group, or a substituted or unsubstituted tert-butyl group. The substituted methyl group is preferably benzyl or p-methoxybenzyl.

R_a1Wherein said substituted or unsubstituted C₁-C₄The alkoxy group of (b) is preferably a substituted or unsubstituted methoxy group, a substituted or unsubstituted ethoxy group, a substituted or unsubstituted n-propoxy group, a substituted or unsubstituted isopropoxy group, a substituted or unsubstituted n-butoxy group, a substituted or unsubstituted isobutoxy group, or a substituted or unsubstituted tert-butoxy group.

R_b1In (b), the C₂-C₄The alkenyl group of (A) is preferably an ethenyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group or a 3-butenyl group.

R_d1Or R_e1In (b), the C₁-C₄The alkyl group of (a) is preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group or a tert-butyl group.

R_d1In (b), the C₁-C₄The alkoxy group of (b) is preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy.

R_d1Wherein said C is substituted by one or more halogens₁-C₄Said halogen in the alkyl group of (a) preferably means fluorine, chlorine, bromine or iodine; said C substituted by one or more halogens₁-C₄C in the alkyl group of (1)₁-C₄The alkyl group of (a) is preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group or a tert-butyl group. Said C substituted by one or more halogens₁-C₄The alkyl group of (A) is preferably

R_e1In (b), the C₆-C₂₀Aryl is preferably phenyl.

The asymmetric allylic substitution reaction may be conventional in the art for such reactions, preferably, only in the general formula I, formula IIIII, formula IV, formula V or formula VI, without further catalyst, such as a copper-based catalyst and/or a palladium-based catalyst. The asymmetric allylic substitution reaction is preferably carried out under gas protection. The gas is preferably an inert gas, such as argon. The organic solvent may be an organic solvent that is conventional in the art, as long as the reaction is not affected, and in the present invention, one or more of an aromatic hydrocarbon solvent, a halogenated hydrocarbon solvent, an ether solvent, an amide solvent, an alkane solvent, and a nitrile solvent are preferred. The aromatic hydrocarbon solvent is preferably toluene. The halogenated hydrocarbon solvent is preferably Dichloromethane (DCM) and/or trichloromethane (CHCl)₃). The ethereal solvent is preferably one or more of Tetrahydrofuran (THF), diethyl ether and 1, 4-dioxane. The alkane solvent is preferably n-hexane. The nitrile solvent is preferably acetonitrile. The base is preferably an organic base and/or an inorganic base. The organic base may be any organic base conventional in the art, preferably 1, 8-diazabicycloundecen-7-ene (DBU), N-Diisopropylethylamine (DIEA), triethylamine (Et)₃N) and 1, 4-diazabicyclo [2.2.2]One or more of octane (DABCO). The inorganic base may be any conventional inorganic base in the art, preferably Cs₂CO₃、K₂CO₃、Na₂CO₃、Li₂CO₃Lithium tert-butoxide (c)^tBuoli), sodium tert-butoxide (^tBuona) and potassium tert-butoxide (^tBuOK). The molar ratio of the metal iridium complex to the compound shown as the formula S1 can be selected according to the conventional molar ratio of the conventional reaction in the field, and is preferably 0.01: 1-0.1: 1. The molar ratio of the base to the compound of formula S1 may be conventional in the art, and is preferably 0.1:1 to 1: 1. The dosage of the solvent does not influence the reaction, and preferably, the volume-mass ratio of the solvent to the compound shown in the formula A is 10mL/g-100 mL/g. The reaction temperature is preferably 0 to 120 ℃, more preferably 25 to 85 ℃. The progress of the reaction can be achieved by the methods known in the artThe reaction is generally terminated when the compound of formula S1 disappears, and the reaction time is preferably 2 to 48 hours.

The invention also provides a benzindole compound shown as the formula P, wherein carbon marked by x is chiral carbon or non-chiral carbon, and when the carbon is chiral carbon, the chiral carbon is S configuration or R configuration;

wherein R is_a1And R_b1The definitions of (A) and (B) are the same as described above; however, the compounds of formula P do not include compounds of any of the following structures:

the compound shown in the formula P is preferably any one of the following compounds:

the above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.

The reagents and starting materials used in the present invention are commercially available.

The positive progress effects of the invention are as follows:

(1) the metal iridium complex containing the chiral triazole carbene is stable in air and convenient to store. The metal iridium complex can be subjected to column chromatography purification, recrystallization and other operations in the air, and has no influence on products. The metal iridium complex is placed in the air for six months, the purity (97 percent) of the metal iridium complex is not changed, when the metal iridium complex is used as a catalyst for catalyzing allyl substitution reaction, the yield and the purity of a target compound are not influenced, and the catalytic effect is the same as that of the new preparation.

(2) The preparation method of the metal iridium complex has the advantages of mild reaction conditions, simple operation, easily obtained raw materials, high yield and simple post-treatment.

(3) The metal iridium complex containing the chiral triazole carbene can be applied to various different types of asymmetric intermolecular allyl substitution reactions and intramolecular substitution reactions catalyzed by metal iridium, achieves high yield, high regioselectivity and high enantioselectivity, can be applied to more complex substrate reactions, and greatly expands the application range of the asymmetric intermolecular allyl substitution reactions and the intramolecular substitution reactions.

Drawings

FIG. 1 is a single crystal structural view of a compound IIIa obtained in example 3.

Detailed Description

The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.

Wherein compounds a, b, c, d, e and f can be prepared according to methods conventional in the art, see in particular (a) chem.commu.2008, 2263.(b) j.org.chem.2005,70,5725.(c) org.biomol.chem.2011,9,2072.(d) org.lett.2008,10,277.(e) angelw.chem.int.ed.2002, 41,1743.(f) j.am.chem.soc.2007,129,10098.

Example 1 Synthesis of a Metal Iridium Complex represented by the general formula I

Under the protection of argon, a dry 250 ml three-neck bottle is added with [ Ir (cod) Cl]₂(336mg,0.5mmol) of a compound represented by the formula a and a base, adding an organic solvent, stirring for reaction for 24 hours, and separating the crude product by column chromatography (ethyl acetate/petroleum ether ═ 1: 5). Specific reaction conditions for compounds Ia-Ic and compound If are shown in Table 1. The preparation methods and conditions of the compounds Id-Ie and Ig-Ik are described in example 1 and Table 1, wherein the molar ratio in Table 1 is [ Ir (cod) X¹]₂: a compound a: molar ratio of the base.

TABLE 1

Compound Ia

Yellow solid, yield: 54% (> 97% purity, nuclear magnetic purity)

¹H NMR(300MHz,CDCl₃)δ8.32(d,J＝7.2Hz,2H),7.49-7.46(m,3H),4.94(AB,J_AB＝15.0Hz,1H),4.80-4.71(m,3H),4.44-4.38(m,2H),3.89(d,J＝6.9Hz,1H),2.85-2.78(m,1H),2.36-1.67(m,8H),1.51-1.22(m,5H),1.06(s,3H),0.95(s,3H),0.88(s,3H).

¹³C NMR(100MHz,CDCl₃)δ181.5,149.3,140.2,128.44,128.38,128.2,124.4,123.9,85.1,84.6,61.4,59.4,54.5,52.0,50.1,47.6,33.2,32.51,32.49,29.9,28.5,25.4,22.0,21.2,11.4.

Elemental analysis: calcd for C₂₇H₃₅N₃ClOIr is C, 50.26; h, 5.47; n,6.51 Experimental value (Found): C,50.26；H,5.43；N,6.38.

Compound Ib

Yellow solid, yield: 44% (> 97% purity, nuclear magnetic purity)

¹H NMR(300MHz,CDCl₃)δ7.03(s,1H),6.90(s,1H),4.90(AB,J_AB＝14.7Hz,1H),4.62-4.53(m,4H),4.41(AB,J_AB＝14.7Hz,1H),3.95(d,J＝6.9Hz,1H),3.05(d,J＝8.4Hz,1H),2.67-2.63(m,1H),2.37(s,3H),2.36(s,3H),2.10-1.89(m,4H),1.84(s,3H),1.71-1.26(m,7H),1.09(d,J＝6.0Hz,1H),1.05(s,3H),0.95(s,3H),0.82(s,3H).

¹³C NMR(75MHz,CDCl₃)δ181.5,148.6,139.3,136.5,136.2,135.4,129.2,128.1,84.8,84.1,84.0,61.0,59.2,53.2,51.5,51.1,50.2,47.7,33.6,33.1,32.7,29.1,29.0,25.1,21.9,21.2,20.6,19.5,17.5,11.4.

Elemental analysis: calcd for C₃₀H₄₁N₃ClOIr is C, 52.42; h, 6.01; n,6.11 Experimental values (Found) C, 52.62; h, 6.03; and N,6.04.

Compound Ic

Yellow solid, yield: 40% (> 97% purity, nuclear magnetic purity)

¹H NMR(400MHz,CD₂Cl₂)δ9.43(s,2H),7.94(s,1H),5.01(AB,J_AB＝13.6Hz,1H),4.95-4.91(m,1H),4.76-4.71(m,1H),4.57(d,J＝4.4Hz,1H),4.43(AB,J_AB＝15.2Hz,1H),4.03-3.98(m,2H),2.85-2.80(m,1H),2.54(t,J＝7.2Hz,1H),2.35-2.27(m,1H),2.13-1.99(m,4H),1.87-1.81(m,1H),1.71(dt,J＝2.8,12.0Hz,1H),1.58-1.55(m,2H),1.51-1.47(m,1H),1.39-1.33(m,1H),1.30-1.26(m,1H),1.04(s,3H),0.90(s,3H),0.87(s,3H).

¹³C NMR(100MHz,CD₂Cl₂)δ186.3,149.9,141.5,131.8(q,J＝33.4Hz),124.9(m),123.9,121.4(m),87.6,87.1,85.4,62.7,59.6,55.0,52.3,51.2,50.2,48.7,34.5,33.0,32.4,31.0,28.1,26.9,21.6,20.6,11.3.

¹⁹F NMR(376MHz,CD₂Cl₂)δ-63.1(s).

Elemental analysis: calcd for C₂₉H₃₃N₃F₆ClOIr is C, 44.58; h, 4.26; n,5.38, Experimental value (Found) C, 44.45; h, 4.34; and N,5.12.

Compound Id

Yellow solid, yield: 57% (> 97% purity, nuclear magnetic purity)

¹H NMR(400MHz,DMSO-d₆)δ8.57(d,J＝8.0Hz,1H),7.36(d,J＝7.6Hz,1H),7.30(t,J＝7.6Hz,1H),7.17(t,J＝7.2Hz,1H),6.02(d,J＝3.2Hz,1H),5.00(AB,J_AB＝15.6Hz,1H),4.94(t,J＝3.6Hz,1H),4.91(AB,J_AB＝16.0Hz,1H),4.60-4.56(m,1H),4.38-4.35(m,1H),3.46-3.41(m,2H),3.30-3.27(m,1H),3.04(AB,J_AB＝16.8Hz,1H)2.13-2.09(m,1H),2.00-1.88(m,3H),1.71-1.58(m,4H).

¹³C NMR(100MHz,DMSO-d₆)δ187.8,149.9,140.8,138.5,128.6,126.6,126.5,125.0,87.8,86.2,78.2,62.0,59.7,54.5,52.9,36.9,33.4,33.0,28.9,28.7,27.6.

¹⁹F NMR(376MHz,DMSO-d₆)δ-138.6(d,J＝23.3Hz),-144.6(d,J＝24.8Hz),-150.3(t,J＝22.6Hz),-161.9(t,J＝23.7Hz),-162.6(t,J＝23.3Hz).

Elemental analysis: calcd for C₂₆H₂₂N₃F₅ClOIr is C, 43.67; h, 3.10; n,5.88 Experimental values (Found) C, 43.62; h, 3.02; n,5.71.

Compound Ie

Yellow solid, yield: 50% (> 97% purity, nuclear magnetic purity)

¹H NMR(300MHz,CDCl₃)δ8.32(d,J＝7.2Hz,2H),7.49-7.46(m,3H),4.94(AB,J_AB＝15.0Hz,1H),4.80-4.71(m,3H),4.44-4.38(m,2H),3.89(d,J＝6.9Hz,1H),3.62(s,3H),2.85-2.78(m,1H),2.36-1.67(m,7H),1.51-1.22(m,5H),1.06(s,3H),0.95(s,3H),0.88(s,3H).

MS(ESI⁺):675(C₂₈H₃₇ClIrN₃O₂[M⁺]).

Compound If

Yellow solid, yield: 60% (> 97% purity, nuclear magnetic purity)

¹H NMR(300MHz,CDCl₃)δ8.32(d,J＝7.2Hz,2H),7.49-7.46(m,3H),4.94(AB,J_AB＝15.0Hz,1H),4.80-4.71(m,3H),4.44-4.38(m,2H),3.89(d,J＝6.9Hz,1H),3.51(s,3H),2.85-2.78(m,1H),2.36-1.67(m,8H),1.51-1.22(m,5H),1.06(s,3H),0.95(s,3H),0.88(s,3H).

MS(ESI⁺):641(C₂₈H₃₈IrN₃O₂[M⁺]).

Compound Ig

Yellow solid, yield: 55% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):745(C₃₅H₃₉IrN₃O[M⁺]).

Compound Ih

Yellow solid, yield: 57% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):745(C₃₅H₃₉IrN₃O[M⁺]).

Compound Ii

Yellow solid, yield: 52% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):651(C₂₇H41₃₉IrN₃O[M⁺]).

Compound Ij

Yellow solid, yield: 50% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):659(C₂₈H41₃₇IrN₃O[M⁺]).

Compound Ik

Yellow solid, yield: 55% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):690(C₂₇H41₃₄ClIrN₄O₃[M⁺]).

Example 2 Synthesis of Metal Iridium Complex represented by general formula II

Adding [ Ir (cod) X into a dry 250 ml three-mouth bottle under the protection of argon^1a]₂(336mg,0.5mmol), the compound represented by the formula b, a base and an organic solvent, stirring for reaction, and separating the crude product by column chromatography (ethyl acetate/petroleum ether: 1: 5). Specific reaction conditions for compounds IIa-IIc and IIf are shown in Table 2. The preparation methods and conditions of the compounds IId to IIe, IIg to IIu are described in reference to example 2 and Table 2, wherein the molar ratios in Table 2 refer to [ Ir (cod) X^1a]₂: compound b: molar ratio of the base.

TABLE 2

Compound IIa

Yellow solid, yield: 55% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):858(C₃₉H₄₂ClIrN₄O₂S[M⁺]).

Compound IIb

Yellow solid, yield: 56% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):900(C₄₂H₄₈ClIrN₄O₂S[M⁺]).

Compound IIc

Yellow solid, yield: 52% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):994(C₄₁H₄₀ClF₆IrN₄O₂S[M⁺]).

Compound IId

Yellow solid, yield: 52% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):948(C₃₉H₃₇ClF₅IrN₄O₂S[M⁺]).

Compound IIe

Yellow solid, yield: 53% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):888(C₃₂H₃₂ClIrN₄O₃S[M⁺]).

Compound IIf

Yellow solid, yield: 53% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):854(C₃₂H₃₂ClIrN₄O₃S[M⁺]).

Compound IIg

Yellow solid, yield: 56% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):974(C₄₈H₅₀ClIrN₄O₂S[M⁺]).

Compound IIh

Yellow solid, yield: 53% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):974(C₄₈H₅₀ClIrN₄O₂S[M⁺]).

Compound IIi

Yellow solid, yield: 53% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):888(C₄₁H₄₈ClIrN₄O₂S[M⁺]).

Compound IIj

Yellow solid, yield: 55% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):880(C₄₀H₅₂ClIrN₄O₂S[M⁺]).

Compound IIk

Yellow solid, yield: 53% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):919(C₄₀H₄₅ClIrN₅O₄S[M⁺]).

Compound IIl

Yellow solid, yield: 59% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):776(C₃₂H₄₄ClIrN₄O₂S[M⁺]).

Compound IIm

Yellow solid, yield: 50% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):762(C₃₅H₄₂ClIrN₄O[M⁺]).

Compound IIn

Yellow solid, yield: 50% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):792(C₃₆H₄₄ClIrN₄O₂[M⁺]).

Compound IIo

Yellow solid, yield: 52% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):898(C₃₇H₄₀ClF₆IrN₄O[M⁺]).

Compound IIp

Yellow solid, yield: 60% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):804(C₃₈H₄₈ClIrN₄O[M⁺]).

Compound IIq

Yellow solid, yield: 54% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):862(C₄₁H₅₄ClIrN₄O₂[M⁺]).

Compound IIr

Yellow solid, yield: 54% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):858(C₃₈H₄₅ClF₃IrN₄O[M⁺]).

Compound IIs

Yellow solid, yield: 55% (> 97% purity data, nuclear magnetic purity)

MS(ESI⁺):894(C₃₇H₄₅ClF₃IrN₄O₂S[M⁺]).

Compound IIt

Yellow solid, yield: 50% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):1244(C₄₄H₄₅ClF₁₇IrN₄O₂S[M⁺]).

Example 3 Synthesis of a Metal Iridium Complex represented by the formula III

Adding [ Ir (cod) X into a dry 250 ml three-mouth bottle under the protection of argon^1b]₂(336mg,0.5mmol) of the compound represented by the formula c, a base and an organic solvent, and stirring to react. The crude product is isolated by column chromatography (ethyl acetate/petroleum ether: 1: 5). See Table 3 for specific reaction conditions for compounds IIIa-IIIc and IIIf. The preparation methods and conditions of the compounds IIId to IIIe refer to example 3 and Table 3, wherein the molar ratio in Table 3 means [ Ir (cod) X^1b]₂: compound c: molar ratio of the base.

TABLE 3

MS(ESI⁺):1244(C₄₄H₄₅ClF₁₇IrN₄O₂S[M⁺]).

Compound IIIa

Yellow solid, yield: 61% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):579(C₂₂H₂₉ClIrN₃O[M⁺]).

The preparation method of the compound IIIa single crystal comprises the following steps: dissolve 100mg of Compound IIIa in 5mL CH₂Cl₂Then n-hexane (2mL) was added dropwise thereto until just turbidity appeared. Adding a drop of CH thereto₂Cl₂The resulting precipitate was dissolved again. The solution was left to stand in a refrigerator at-30 ℃ until the compound IIIa single crystal was formed.

Crystal data in a single crystal X-ray diffraction spectrum using a radiation source of Cu-K α, the crystal is monoclinic, space group is P21, and unit cell parameters are:α＝90°

β＝92.5300(10)°

γ＝90°

cell volumeThe number of asymmetric units in the unit cell, Z, is 2.

Compound IIIb

Yellow solid, yield: 63% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):621(C₂₅H₃₅ClIrN₃O[M⁺]).

Compound IIIc

Yellow solid, yield: 60% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):715(C₂₄H₂₇ClF₆IrN₃O[M⁺]).

Compound IIId

Yellow solid, yield: 60% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):609(C₂₃H₃₁ClF₆IrN₃O₂[M⁺]).

Compound IIIe

Yellow solid, yield: 62% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):669(C₂₂H₂₄ClF₅IrN₃O[M⁺]).

Compound IIIf

Yellow solid, yield: 62% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):665(C₂₃H₂₇F₅IrN₃O[M⁺]).

Example 4 Synthesis of Metal Iridium Complex represented by general formula IV

Adding [ Ir (cod) X into a dry 250 ml three-mouth bottle under the protection of argon^1c]₂(336mg,0.5mmol), a compound represented by the formula d, a base and an organic solvent, stirring for reaction, and separating the crude product by column chromatography (ethyl acetate/petroleum ether: 1: 5). See table 4 for specific reaction conditions for compounds IVa-IVc and compound IVf. The preparation methods and conditions of the compounds IVd-IVe, IVg-IVi refer to example 4 and Table 4, wherein the molar ratio in Table 4 refers to [ Ir (cod) X^1c]₂: a compound d: molar ratio of the base.

TABLE 4

Compound VIa

Yellow solid, yield: 53% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):821(C₃₈H₅₁ClIrN₃OSi[M⁺]).

Compound VIb

Yellow solid, yield: 57% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):863(C₄₁H₅₇ClIrN₃OSi[M⁺]).

Compound VIc

Yellow solid, yield: 59% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):957(C₄₀H₄₉ClF₆IrN₃OSi[M⁺]).

Compound VId

Yellow solid, yield: 59% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):851(C₃₉H₅₃ClIrN₃O₂Si[M⁺]).

Compound VIe

Yellow solid, yield: 59% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):911(C₃₈H₄₆ClF₅IrN₃OSi[M⁺]).

Compound VIf

Yellow solid, yield: 53% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):817(C₃₉H₅₄ClIrN₃O₂Si[M⁺]).

Compound VIg

Yellow solid, yield: 53% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):859(C₄₂H₆₀ClIrN₃O₂Si[M⁺]).

Compound VIh

Yellow solid, yield: 53% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):641(C₂₆H₄₀ClFIrN₃O₂[M⁺]).

Compound VIi

Yellow solid, yield: 53% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):641(C₂₆H₄₀ClFIrN₃O₂[M⁺]).

Example 5 Synthesis of metallic Iridium Complex represented by formula V

Adding [ Ir (cod) X into a dry 250 ml three-mouth bottle under the protection of argon^1d]₂(336mg,0.5mmol), a compound represented by the formula e, a base and an organic solvent, stirring to react, and separating the crude product by column chromatography (ethyl acetate/petroleum ether: 1: 5). The specific reaction conditions for compounds Va-Vc and compound Vf are shown in Table 5. The compound Vd-Ve, the preparation method and conditions of compound Vg refer to example 5 and Table 5, wherein the molar ratio in Table 5 refers to [ Ir (cod) X^1d]₂: compound e: molar ratio of the base.

TABLE 5

Compound Va

Yellow solid, yield: 53% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):659(C₂₈H₃₇ClIrN₃O[M⁺]).

Compound Vb

Yellow solid, yield: 55% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):701(C₃₁H₄₁ClIrN₃O[M⁺]).

Compound Vc

Yellow solid, yield: 55% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):795(C₃₀H₃₅ClF₆IrN₃O[M⁺]).

Compound Vd

Yellow solid, yield: 55% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):689(C₂₉H₃₉ClIrN₃O₂[M⁺]).

Compound Ve

Yellow solid, yield: 55% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):749(C₂₈H₃₂ClF₅IrN₃O[M⁺]).

Compound Vf

Yellow solid, yield: 55% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):655(C₂₉H₄₀IrN₃O₂[M⁺]).

Compound Vg

Yellow solid, yield: 55% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):595(C₂₃H₃₃IrN₃O[M⁺]).

Example 6 Synthesis of Metal Iridium Complex represented by general formula VI

Adding [ Ir (cod) X into a dry 250 ml three-mouth bottle under the protection of argon^1e]₂(336mg,0.5mmol) of a compound represented by the formula f, a base and an organic solvent, and the crude product is separated by column chromatography (ethyl acetate/petroleum ether: 1: 5). The specific reaction conditions for compounds VIa-VIc and compound VIf are shown in table 6. The preparation method and conditions of the compound VId-VIe refer to example 6 and Table 6, wherein the molar ratio in Table 6 is [ Ir (cod) X^1e]₂: a compound f: molar ratio of the base.

TABLE 6

Compound VIa

Yellow solid, yield: 55% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):671(C₂₉H₃₇ClIrN₃O[M⁺]).

Compound VIb

Orange solid, yield: 51% (> 97% purity, nuclear magnetic purity)

¹H NMR(400MHz,CD₂Cl₂)δ8.43(d,J＝6.0Hz,1H),7.36-7.32(m,3H),7.07(s,1H),6.95(s,1H),6.91(d,J＝3.2Hz,1H),4.92(AB,J_AB＝16.0Hz,1H),4.83(AB,J_AB＝16.0Hz,1H),4.74-4.73(m,1H),4.60-4.58(m,1H),4.47-4.43(m,1H),3.34(dd,J＝4.0,16.8Hz,1H),3.23-3.15(m,2H),2.85(t,J＝6.8Hz,1H),2.37(s,6H),2.27-2.18(m,1H),2.15-2.08(m,1H),1.88(s,3H),1.88-1.86(m,1H),1.69-1.63(m,1H),1.54-1.48(m,3H),1.40-1.38(m,1H).

¹³C NMR(100MHz,CD₂Cl₂)δ182.1,148.4,140.8,140.1,139.5,136.9,136.7,136.1,129.6,128.9,128.6,126.9,126.0,125.6,87.4,84.6,79.0,62.4,61.2,56.5,52.7,37.7,34.6,33.0,30.3,28.1,21.3,19.7,17.9.

Compound VIc

Yellow solid, yield: 59% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):807(C₃₁H₃₅ClF₆IrN₃O[M⁺]).

Compound VId

Yellow solid, yield 59% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):701(C₃₀H₃₉ClF₆IrN₃O[M⁺]).

Compound VIe

Yellow solid, yield: 57% (> 97% purity, nuclear magnetic purity)

¹³C NMR(100MHz,DMSO-d₆)δ187.8,149.9,140.8,138.5,128.6,126.6,126.5,125.0,87.8,86.2,78.2,62.0,59.7,54.5,52.9,36.9,33.4,33.0,28.9,28.7,27.6；¹⁹F NMR(376MHz,DMSO-d₆)δ-138.6(d,J＝23.3Hz),-144.6(d,J＝24.8Hz),-150.3(t,J＝22.6Hz),-161.9(t,J＝23.7Hz),-162.6(t,J＝23.3Hz).

Compound VIf

Yellow solid, yield: 60% (> 97% purity, nuclear magnetic purity)

MS(ESI⁺):684(C₃₁H₄₅IrN₃O₂[M⁺]).

Effect example 1 Synthesis of Compound represented by the general formula P

General reaction operation: to a Schlenk tube, under protection of argon, substrate S1(75.6mg,0.2mmol), metallo-iridium complex catalyst (3.2mg,0.01mmol,5 mol%) and base (3.0mg,0.02mmol) were added in 2.0mL of dichloromethane (CH)₂Cl₂) The reaction was stirred at room temperature for 6 hours. After completion of the TLC tracing reaction, the reaction mixture was filtered through celite, and the solvent was removed under reduced pressure and purified by column chromatography (petroleum ether/ethyl acetate: 5/1). The ee of the product was determined by HPLC. Wherein, the conditions of the substrate S1, the catalyst, the alkali and the like are concretely shown in Table 7, and the molar ratio in Table 7 refers to S1: alkali: molar ratio of catalyst. In table 7, the molar ratio is S1: alkali: molar ratio of catalyst.

TABLE 7

Compound P1

Light yellow oil, yield: 81% and an ee value of 92% [ Daicel Chiralcel OD-H, hexane (hexane)/2-propanol (2-propanol) ═ 90/10, v ═ 1.0ml · min^-1,λ＝254nm,t(minor)＝20.38min,t(major)＝31.75min].

[α]_D ²⁰+6.4(c1.00,CH₂Cl₂).

¹H NMR(300MHz,CDCl₃)δ3.43(d,J＝12.6Hz,1H),3.93(dd,J＝12.6,4.5Hz,1H),4.54-4.68(m,2H),4.87-5.00(m,2H),5.08(d,J＝10.5Hz,1H),5.73(ddd,J＝16.8,10.2,5.4Hz,1H),7.15(t,J＝6.9Hz,1H),7.21-7.38(m,8H),7.72(d,J＝7.8Hz,1H).

Compound P2

Yellow solid, yield: 77%, ee value 91% [ Daicel ChiralpakAD-H, hexane (hexane)/2-propanol (2-propanol) ═ 80/20, v ═ 1.0ml · min^-1,λ＝254nm,t(major)＝26.51min,t(minor)＝33.90min].

[α]_D ¹⁶+8.7(c1.00,CH₂Cl₂).

¹H NMR(300MHz,CDCl₃)δ3.45(dd,J＝12.6,2.1Hz,1H),3.94(dd,J＝12.9,5.1Hz,1H),4.57(d,J＝16.8Hz,2H),4.59(d,J＝14.7Hz,2H),5.10(d,J＝9.9Hz,1H),5.70(ddd,J＝16.8,10.5,5.4Hz,1H),7.12(d,J＝9.0Hz,1H),7.24-7.40(m,7H),7.85(s,1H)；¹³C NMR(75MHz,CDCl₃)δ49.4,49.5,53.0,105.8,111.5,113.9,118.3,125.0,127.5,127.8,128.5,128.6,128.9,129.6,133.5,134.7,136.1,159.3.

IR (film) < v >_max(cm^-1)＝3064,1639,1547,1448,1429,1251,1173,933,802,732,697.

HRMS-ESI calculated value (Calcd for) C₂₀H₁₈BrN₂O(M⁺+ H) 381.0597, Experimental value (Found) 381.0599.

m.p.＝135-136℃.

Compound P3

Light yellow oil, yield: 78%, ee value 92% [ Daicel ChiralpakAD-H, hexane (hexane)/2-propanol (2-propanol) ═ 80/20, v ═ 1.0ml · min^-1,λ＝254nm,t(major)＝17.92min,t(minor)＝24.91min].

[α]_D ¹⁷+12.3(c1.00,CH₂Cl₂).

¹H NMR(300MHz,CDCl₃)δ3.45(d,J＝13.2Hz,1H),3.93(dd,J＝13.2,4.8Hz,1H),4.60(d,J＝14.7Hz,1H),4.62(d,J＝17.1Hz,1H),4.83-4.99(m,2H),5.12(d,J＝10.5Hz,1H),5.72(ddd,J＝15.6,9.9,5.1Hz,1H),7.12(d,J＝8.7Hz,1H),7.25(s,1H),7.27-7.38(m,6H),7.63(d,J＝8.4Hz,1H)；¹³C NMR(75MHz,CDCl₃)δ49.5,49.6,53.0,106.7,110.0,118.4,121.7,123.6,125.9,127.8,128.5,128.6,129.3,130.5,133.4,136.1,136.4,159.5.

IR (film) < v >_max(cm^-1)＝2918,2850,1652,1645,1564,1471,1347,1057,951,735,700.

HRMS-ESI calculated value (Calcd for) C₂₀H₁₈ClN₂O(M⁺+ H) 337.1102, Experimental value (Found) 337.1104.

Compound P4

Yellow solid, yield: 84% and an ee value of 89% [ Daicel ChiralpakAD-H, hexane (hexane)/2-propanol (2-propanol) ═ 80/20, v ═ 1.0ml · min^-1,λ＝254nm,t(major)＝20.09min,t(minor)＝25.97min].

[α]_D ¹⁷+3.1(c1.00,CH₂Cl₂).

¹H NMR(400MHz,CDCl₃)δ3.44(d,J＝12.0,1.6Hz,1H),3.92(dd,J＝12.8,4.4Hz,1H),4.57-4.64(m,2H),4.89-4.96(m,2H),5.09(d,J＝10.4Hz,1H),5.72(ddd,J＝16.8,10.4,5.2Hz,1H),7.03(dt,J＝8.8,2.4Hz,1H),7.17(dd,J＝9.2,4.4Hz,1H),7.24-7.36(m,7H).

¹³C NMR(75MHz,CDCl₃)δ49.5,49.6,53.1,106.2,106.3,106.8,107.1,110.9,113.6,118.2,127.5,127.6,127.7,128.4,128.6,130.1,132.8,133.7,136.2,156.9,159.3,159.4.

IR (film) < v >_max(cm^-1)＝3030,2922,1640,1549,1496,1466,1361,1250,1189,928,800,735.

HRMS-ESI calculated value (Calcd for) C₂₀H₁₈FN₂O(M⁺+ H) 321.1398, Experimental value (Found) 321.1398.

m.p.＝127-128℃.

Compound P5

Yellow solid, yield: 86% and an ee value of 93% [ Daicel ChiralpakAD-H, hexane (hexane)/2-propanol (2-propanol) ═ 80/20, v ═ 1.0ml · min^-1,λ＝230nm,t(major)＝24.02min,t(minor)＝29.46min].

[α]_D ²¹+7.0(c1.00,CH₂Cl₂).

¹H NMR(400MHz,CDCl₃)δ2.43(s,3H),3.42(dd,J＝12.4,2.0Hz,1H),3.92(dd,J＝12.8,4.8Hz,1H),4.57-4.64(m,2H),4.89-4.97(m,2H),5.09(d,J＝10.4Hz,1H),5.72(ddd,J＝15.6,10.0,5.2Hz,1H),7.09-7.16(m,2H),7.24-7.36(m,6H),7.50(s,1H).

¹³C NMR(75MHz,CDCl₃)δ21.4,49.5,49.7,52.9,106.1,109.7,118.0,122.1,126.5,127.6,127.7,128.4,128.5,128.6,130.1,133.9,134.7,136.4,159.9.

IR (film) < v >_max(cm^-1)＝3053,2919,1635,1549,1428,1357,1253,1184,934,809,737,697.

HRMS-ESI calculated value (Calcd for) C₂₁H₂₁N₂O(M⁺+ H) 317.1648, Experimental value (Found) 317.1652.

m.p.＝142-143℃.

Compound P6

White solid, yield: 87% and an ee value of 94% [ Daicel ChiralpakAD-H, hexane (hexane)/2-propanol (2-propanol) ═ 80/20, v ═ 1.0ml · min^-1,λ＝230nm,t(major)＝28.39min,t(minor)＝45.66min].

[α]_D ²⁰+3.8(c1.00,CH₂Cl₂).

¹H NMR(400MHz,CDCl₃)δ3.42(dd,J＝12.4,2.0Hz,1H),3.84(s,3H),3.92(dd,J＝12.4,4.8Hz,1H),4.61(d,J＝14.8Hz,1H),4.62(d,J＝16.8Hz,1H),4.87-4.96(m,2H),5.08(d,J＝10.4Hz,1H),5.72(ddd,J＝15.6,10.4,5.2Hz,1H),6.96(dd,J＝9.2,3.2Hz,1H),7.10-7.16(m,2H),7.24-7.34(m,6H).

¹³C NMR(75MHz,CDCl₃)δ49.4,49.7,53.1,55.6,102.8,106.1,110.9,116.0,118.0,127.6,127.8,128.4,128.6,129.0,131.6,134.0,136.4,154.7,159.8.

IR (film) < v >_max(cm^-1)＝3065,2935,1633,1545,1358,1230,1215,1034,834,813,703.

HRMS-ESI calculated value (Calcd for) C₂₁H₂₁N₂O₂(M⁺+ H) 333.1598, Experimental value (Found) 333.1600.

m.p.＝148-149℃.

Compound P7

Colorless oil, yield: 75%, ee value 92% [ Daicel ChiralpakAD-H, hexane (hexane)/2-propanol (2-propanol) ═ 80/20, v ═ 1.0ml · min^-1,λ＝230nm,t(major)＝18.96min,t(minor)＝24.65min].

[α]_D ¹⁶+16.2(c1.00,CH₂Cl₂).

¹H NMR(400MHz,CDCl₃)δ3.44(d,J＝12.9Hz,1H),3.92(dd,J＝12.6,4.5Hz,1H),4.59(d,J＝14.7Hz,1H),4.61(d,J＝16.8Hz,1H),4.85-4.98(m,2H),5.12(d,J＝10.8Hz,1H),5.71(ddd,J＝16.2,10.2,5.1Hz,1H),7.20-7.38(m,7H),7.41(s,1H),7.57(d,J＝8.4Hz,1H).

¹³C NMR(100MHz，CDCl₃)δ49.5，49.6，53.0，106.7，113.0，118.3，118.4，123.9，124.2，126.2,127.8,128.5,128.6,129.2,133.4,136.1,136.8,159.4.

IR (film) < v >_max(cm^-1) 3080,2925,1644,1545,1494,1430,1355,1270,1149,928,821,744; HRMS-ESI calculated value (Calcd for) C₂₀H₁₈BrN₂O(M⁺+ H) 381.0597, Experimental value (Found) 381.0599.

Compound P8

Yellow solid, yield: 75%, ee value 91% [ Daicel ChiralpakAD-H, hexane (hexane)/2-propanol (2-propanol) ═ 80/20, v ═ 1.0ml · min^-1,λ＝230nm,t(major)＝23.53min,t(minor)＝29.22min]；[α]_D ²⁶+10.2(c1.00,CH₂Cl₂).

¹H NMR(400MHz,CDCl₃)δ3.45(dd,J＝12.6,1.8Hz,1H),3.94(dd,J＝12.9,5.1Hz,1H),4.53-4.64(m,2H),4.89-4.98(m,2H),5.10(d,J＝9.9Hz,1H),5.71(ddd,J＝15.6,10.5,5.4Hz,1H),7.13-7.19(m,1H),7.20-7.38(m,7H),7.68(s,1H).

¹³C NMR(75MHz,CDCl₃)δ49.5,49.6,53.0,105.9,111.1,118.3,121.9,125.0,126.4,127.8,128.2,128.5,128.6,129.8,133.5,134.4,136.1,159.4.

IR (film) < v >_max(cm^-1)＝3086,2924,1649,1548,1474,1420,1250,1061,919,801,745.

HRMS-ESI calculated value (Calcd for) C₂₀H₁₈ClN₂O(M⁺+ H) 337.1102 Experimental values (Found) 337.1108 m.p.127 and 128 ℃.

Compound P9:

yellow oil, yield: 89% ee value 89% [ Daicel ChiralpakAD-H, hexane (hexane)/2-propanol (2-propanol) ═ 80/20, v ═ 1.0ml · min^-1,λ＝230nm,t(major)＝14.51min,t(minor)＝19.40min].

[α]_D ²⁵+21.9(c1.00,CH₂Cl₂).

¹H NMR(400MHz,CDCl₃)δ3.42(dd,J＝12.9,2.1Hz,1H),3.83(s,3H),3.92(dd,J＝12.6,4.5Hz,1H),4.59(d,J＝15.0Hz,1H),4.61(d,J＝16.5Hz,1H),5.10(d,J＝9.9Hz,1H),5.72(ddd,J＝15.6,10.5,5.1Hz,1H),6.63(s,1H),6.82(dd,J＝8.7,2.1Hz,1H),7.24-7.37(m，6H)，7.59(d，J＝8.7Hz，1H).

¹³C NMR(75MHz,CDCl₃)δ49.4,49.7,52.8,55.5,92.3,107.0,111.7,118.1,121.7,123.5,127.6,127.7,128.5,128.6,133.7,136.5,137.1,158.3,159.9.

IR (film) < v >_max(cm^-1)＝3292,2924,1640,1544,1496,1312,1210,1028,812,703.

HRMS-ESI calculated value (Calcd for) C₂₁H₂₁N₂O₂(M⁺+ H) 333.1598, Experimental value (Found) 333.1599.

Compound P10

White solid, yield: 77% and an ee value of 90% [ Daicel Chiralcel OD-H, hexane (hexane)/2-propanol (2-propanol) ═ 80/20, v ═ 1.0ml · min^-1,λ＝230nm,t(minor)＝13.30min,t(major)＝27.78min].

[α]_D ¹⁸-13.9(c1.00,CH₂Cl₂).¹H NMR(400MHz,CDCl₃)δ3.15(s,3H),3.50(dd,J＝12.8,2.4Hz,1H),4.08(dd,J＝12.8,4.8Hz,1H),4.76(d,J＝16.0Hz,1H),4.99-5.05(m,1H),5.17(d,J＝10.0Hz,1H),5.95(ddd,J＝15.6,10.0,5.6Hz,1H),7.12-7.18(m,1H),7.24-7.32(m,3H),7.71(d,J＝8.0Hz,1H).

¹³C NMR(100MHz,CDCl₃)δ34.4,52.7,53.0,106.1,110.0,118.2,120.7,122.6,124.4,127.4,128.7,133.8,136.1,160.0.

IR (film) < v >_max(cm^-1)＝3083,2926,1644,1551,1454,1399,1326,1268,936,812,752,744.

HRMS-ESI calculated value (Calcd for) C₁₄H₁₅N₂O(M⁺+ H) 227.1179 Experimental values (Found) 227.1175;

m.p.＝127-128℃.

compound P11

White solid, yield: 82% and an ee value of 92% [ Daicel Chiralcel OD-H, hexane (hexane)/2-propanol (2-propanol) ═ 85/15, v ═ 1.0ml · min^-1,λ＝230nm,t(minor)＝16.68min,t(major)＝34.39min]；[α]_D ²⁷-22.1(c1.00,CH₂Cl₂).

¹H NMR(300MHz，CDCl₃)δ3.51(dd，J＝12.9，2.4Hz，1H)，3.91-4.04(m，2H)，4.40(dd,J＝15.6,5.7Hz,1H),4.69(d,J＝17.4Hz,1H),4.98-5.08(m,1H),5.16(d,J＝10.2Hz,1H),5.25(d,J＝9.3Hz,1H),5.28(d,J＝17.1Hz,1H),5.71-5.98(m,2H),7.11-7.20(m,1H),7.23-7.35(m,3H),7.71(d,J＝7.8Hz,1H).

¹³C NMR(100MHz,CDCl₃)δ48.4,49.6,52.9,106.4,110.0,118.2,118.6,120.7,122.6,124.5,127.4,128.6,132.5,133.8,136.0,159.5.

IR (film) < v >_max(cm^-1)＝3050,2906,1641,1544,1456,1356,1243,1145,933,921,815,756.

HRMS-ESI calculated value (Calcd for) C₁₆H₁₇N₂O(M⁺+ H) 253.1335, Experimental value (Found) 253.1336.

m.p.＝115-116℃.

Compound P12

Light yellow oil, yield: 95% and an ee value of 93% [ Daicel ChiralpakAD-H, hexane (hexane)/2-propanol (2-propanol) ═ 80/20, v ═ 1.0ml · min^-1,λ＝230nm,t(major)＝24.83min,t(minor)＝34.87min].

[α]_D ¹⁷-4.4(c1.00,CH₂Cl₂).

¹H NMR(300MHz,CDCl₃)δ3.43(d,J＝13.2Hz,1H),3.78(s,3H),3.94(dd,J＝12.9,5.1Hz,1H),4.52(d,J＝14.7Hz,1H),4.58(d,J＝17.7Hz,1H),4.89(d,J＝14.7Hz,1H),4.94-5.00(m,1H),5.07(d,J＝10.5Hz,1H),5.71(ddd,J＝15.9,10.5,5.4Hz,1H),6.85(d,J＝8.4Hz,1H),7.14(t,J＝7.8Hz,1H),7.21-7.33(m,4H),7.34(s,1H),7.72(d,J＝7.8Hz,1H).

Effect example 2

General reaction operation: to a Schlenk tube, under protection of argon, substrate S1(75.6mg,0.2mmol), 3a (5.8mg,0.01mmol,5 mol%) and DBU (3.0mg,0.02mmol) were added in 2.0mL of dichloromethane (CH)₂Cl₂) The reaction was stirred at room temperature for 6 hours. After completion of the TLC tracing reaction, the reaction mixture was filtered through celite, and the solvent was removed under reduced pressure and purified by column chromatography (petroleum ether/ethyl acetate: 5/1). The ee of the product was determined by HPLC. In table 8, the molar ratio is S1: alkali: molar ratio of catalyst.

TABLE 8

Compound P13

Light yellow oil, yield: 83% and an ee value of 99% [ Daicel Chiralcel OD-H, hexane (hexane)/2-propanol (2-propanol) ═ 90/10, v ═ 1.0ml · min^-1,λ＝254nm,t(major)＝19.86min,t(minor)＝34.51min]；[α]_D ²⁸-6.5(c1.00,CH₂Cl₂).

Compound P14

Yellow solid, yield: 87% and an ee value of 98% [ Daicel ChiralpakAD-H, hexane (hexane)/2-propanol (2-propanol) ═ 80/20, v ═ 1.0ml · min^-1,λ＝254nm,t(minor)＝23.86min,t(major)＝30.53min].

[α]_D ²⁶-10.2(c1.00,CH₂Cl₂).

¹H NMR(300MHz,CDCl₃)δ3.45(dd,J＝12.6,2.1Hz,1H),3.94(dd,J＝12.9,5.1Hz,1H),4.57(d,J＝16.8Hz,2H),4.59(d,J＝14.7Hz,2H),5.10(d,J＝9.9Hz,1H),5.70(ddd,J＝16.8,10.5,5.4Hz,1H),7.12(d,J＝9.0Hz,1H),7.24-7.40(m,7H),7.85(s,1H).

¹³C NMR(75MHz,CDCl₃)δ49.4,49.5,53.0,105.8,111.5,113.9,118.3,125.0,127.5,127.8,128.5,128.6,128.9,129.6,133.5,134.7,136.1,159.3.

IR (film) < v >_max(cm^-1) 3064,1639,1547,1448,1429,1251,1173,933,802,732,697; HRMS-ESI calculated value (Calcd for) C₂₀H₁₈BrN₂O(M⁺+ H) 381.0597, Experimental value (Found) 381.0599.

m.p.＝135-136℃.

Compound P15

Light yellow oil, yield: 91%, ee value 98% [ Daicel ChiralpakAD-H, hexane (hexane)/2-propanol (2-propanol) ═ 80/20, v ═ 1.0ml · min^-1,λ＝254nm,t(minor)＝16.81min,t(major)＝22.81min].

[α]_D ²⁶-13.7(c1.00,CH₂Cl₂).

¹H NMR(300MHz,CDCl₃)δ3.45(d,J＝13.2Hz,1H),3.93(dd,J＝13.2,4.8Hz,1H),4.60(d,J＝14.7Hz,1H),4.62(d,J＝17.1Hz,1H),4.83-4.99(m,2H),5.12(d,J＝10.5Hz,1H),5.72(ddd,J＝15.6,9.9,5.1Hz,1H),7.12(d,J＝8.7Hz,1H),7.25(s,1H),7.27-7.38(m,6H),7.63(d,J＝8.4Hz,1H).

¹³C NMR(75MHz,CDCl₃)δ49.5,49.6,53.0,106.7,110.0,118.4,121.7,123.6,125.9,127.8，128.5，128.6，129.3，130.5，133.4，136.1，136.4，159.5.

Compound P16

Yellow solid, yield: 84% and an ee value of 98% [ Daicel ChiralpakAD-H, hexane (hexane)/2-propanol (2-propanol) ═ 80/20, v ═ 1.0ml · min^-1,λ＝254nm,t(minor)＝18.42min,t(minor)＝23.58min]；[α]_D ²³-3.7(c1.00,CH₂Cl₂).

¹H NMR(400MHz,CDCl₃)δ3.44(d,J＝12.0,1.6Hz,1H),3.92(dd,J＝12.8,4.4Hz,1H),4.57-4.64(m,2H),4.89-4.96(m,2H),5.09(d,J＝10.4Hz,1H),5.72(ddd,J＝16.8,10.4,5.2Hz,1H),7.03(dt,J＝8.8,2.4Hz,1H),7.17(dd,J＝9.2,4.4Hz,1H),7.24-7.36(m,7H)；¹³C NMR(75MHz,CDCl₃)δ49.5,49.6,53.1,106.2,106.3,106.8,107.1,110.9,113.6,118.2,127.5,127.6,127.7,128.4,128.6,130.1,132.8,133.7,136.2,156.9,159.3,159.4.

m.p.＝127-128℃.

Compound P17

Yellow solid, yield: 87% and an ee value of 99% [ Daicel ChiralpakAD-H, hexane (hexane)/2-propanol (2-propanol) ═ 80/20, v ═ 1.0ml · min^-1,λ＝230nm,t(minor)＝22.30min,t(major)＝27.39min].

[α]_D ²⁵-5.8(c1.00,CH₂Cl₂).

¹H NMR(400MHz,CDCl₃)δ2.43(s,3H),3.42(dd,J＝12.4,2.0Hz,1H),3.92(dd,J＝12.8,4.8Hz,1H),4.57-4.64(m,2H),4.89-4.97(m,2H),5.09(d,J＝10.4Hz,1H),5.72(ddd,J＝15.6，10.0，5.2Hz，1H)，7.09-7.16(m，2H)，7.24-7.36(m，6H)，7.50(s，1H)；¹³C NMR(75MHz,CDCl₃)δ21.4,49.5,49.7,52.9,106.1,109.7,118.0,122.1,126.5,127.6,127.7,128.4,128.5,128.6,130.1,133.9,134.7,136.4,159.9.

m.p.＝142-143℃.

Compound P18

White solid, yield: 79% ee value 98% [ Daicel ChiralpakAD-H, hexane (hexane)/2-propanol (2-propanol) ═ 80/20, v ═ 1.0ml · min^-1,λ＝230nm,t(minor)＝26.64min,t(major)＝30.33min].

[α]_D ²³-4.9(c1.00,CH₂Cl₂).

m.p.＝148-149℃.

Compound P19

Colorless oil, yield: 91%, ee value 99% [ Daicel ChiralpakAD-H, hexane/2-propanol (2-propanol) ═ 80/20, v ═ 1.0 ml/min^-1，λ＝230nm，t(minor)＝18.25min，t(major)＝23.05min].

[α]_D ²⁸-16.6(c1.00,CH₂Cl₂).

¹³C NMR(100MHz,CDCl₃)δ49.5,49.6,53.0,106.7,113.0,118.3,118.4,123.9,124.2,126.2,127.8,128.5,128.6,129.2,133.4,136.1,136.8,159.4.

IR (film) < v >_max(cm^-1)＝3080,2925,1644,1545,1494,1430,1355,1270,1149,928,821,744.

Compound P20

Yellow solid, yield: 86% and an ee value of 98% [ Daicel ChiralpakAD-H, hexane (hexane)/2-propanol (2-propanol) ═ 80/20, v ═ 1.0ml · min^-1,λ＝230nm,t(minor)＝21.57min,t(major)＝26.72min].

[α]_D ²⁶-9.9(c1.00,CH₂Cl₂).

IR (film) < v >_max(cm^-1) 3086,2924,1649,1548,1474,1420,1250,1061,919,801,745; HRMS-ESI calculated value (Calcd for) C₂₀H₁₈ClN₂O(M⁺+ H) 337.1102, Experimental value (Found) 337.1108.

m.p.＝127-128℃.

Compound P21

Yellow oil, yield: 77%, ee value 98% [ Daicel ChiralpakAD-H, hexane (hexane)/2-propanol (2-propanol) ═ 80/20, v ═ 1.0ml · min^-1,λ＝230nm,t(minor)＝22.72min,t(major)＝29.24min].

[α]_D ²²-24.2(c1.00,CH₂Cl₂).

¹H NMR(400MHz,CDCl₃)δ3.42(dd,J＝12.9,2.1Hz,1H),3.83(s,3H),3.92(dd,J＝12.6,4.5Hz,1H),4.59(d,J＝15.0Hz,1H),4.61(d,J＝16.5Hz,1H),5.10(d,J＝9.9Hz,1H),5.72(ddd,J＝15.6,10.5,5.1Hz,1H),6.63(s,1H),6.82(dd,J＝8.7,2.1Hz,1H),7.24-7.37(m,6H),7.59(d,J＝8.7Hz,1H).

IR (film) < v >_max(cm^-1)＝3292,2924,1640,1544,1496,1312,1210,1028,812,703.

Compound P22

White solid, yield: 81% ee value 96% [ Daicel Chiralcel OD-H, hexane (hexane)/2-propanol (2-propanol) ═ 80/20, v ═ 1.0ml · min^-1,λ＝230nm,t(major)＝11.80min,t(minor)＝25.48min].

[α]_D ²³+15.8(c1.00,CH₂Cl₂).¹H NMR(400MHz,CDCl₃)δ3.15(s,3H),3.50(dd,J＝12.8,2.4Hz,1H),4.08(dd,J＝12.8,4.8Hz,1H),4.76(d,J＝16.0Hz,1H),4.99-5.05(m,1H),5.17(d,J＝10.0Hz,1H),5.95(ddd,J＝15.6,10.0,5.6Hz,1H),7.12-7.18(m,1H),7.24-7.32(m,3H),7.71(d,J＝8.0Hz,1H).

HRMS-ESI calculated value (Calcd for) C₁₄H₁₅N₂O(M⁺+ H) 227.1179, Experimental value (Found) 227.1175.

m.p.＝127-128℃.

Compound P23

White solid, yield: 74% and an ee value of 98% [ Daicel Chiralcel OD-H, hexane (hexane)/2-propanol (2-propanol) ═ 85/15, v ═ 1.0ml · min^-1,λ＝230nm,t(major)＝15.58min,t(minor)＝31.85min].

[α]_D ²⁵+29.7(c1.00,CH₂Cl₂).

¹H NMR(300MHz,CDCl₃)δ3.51(dd,J＝12.9,2.4Hz,1H),3.91-4.04(m,2H),4.40(dd,J＝15.6,5.7Hz,1H),4.69(d,J＝17.4Hz,1H),4.98-5.08(m,1H),5.16(d,J＝10.2Hz,1H),5.25(d,J＝9.3Hz,1H),5.28(d,J＝17.1Hz,1H),5.71-5.98(m,2H),7.11-7.20(m,1H),7.23-7.35(m,3H),7.71(d,J＝7.8Hz,1H).

m.p.＝115-116℃.

Compound P24

Light yellow oil, yield: 89% ee value of 99% [ Daicel ChiralpakAD-H, hexane (hexane)/2-propanol (2-propanol) ═ 80/20, v ═ 1.0ml · min^-1,λ＝230nm,t(minor)＝23.23min,t(major)＝35.43min].

[α]_D ²⁸+4.0(c1.00,CH₂Cl₂).

¹H NMR(300MHz，CDCl₃)δ3.43(d，J＝13.2Hz，1H)，3.78(s，3H)，3.94(dd，J＝12.9，5.1Hz,1H),4.52(d,J＝14.7Hz,1H),4.58(d,J＝17.7Hz,1H),4.89(d,J＝14.7Hz,1H),4.94-5.00(m,1H),5.07(d,J＝10.5Hz,1H),5.71(ddd,J＝15.9,10.5,5.4Hz,1H),6.85(d,J＝8.4Hz,1H),7.14(t,J＝7.8Hz,1H),7.21-7.33(m,4H),7.34(s,1H),7.72(d,J＝7.8Hz,1H).

Effect example 3 IIIa was left to stand in the air for 6 months and tested for its catalytic action in the synthesis of the compound represented by the formula P

General reaction operation: to a Schlenk tube, under protection of argon, substrate S1(75.6mg,0.2mmol), IIIa (5.8mg,0.01mmol,5 mol% after six months in air) and DBU (3.0mg,0.02mmol) in 2.0mL of dichloromethane (CH)₂Cl₂) The reaction was stirred at room temperature for 6 hours. After completion of the TLC tracing reaction, the reaction mixture was filtered through celite, and the solvent was removed under reduced pressure and purified by column chromatography (petroleum ether/ethyl acetate: 5/1). The ee of the product was determined by HPLC.

Compound P25

Light yellow oil, yield: 82% and an ee value of 99% [ Daicel Chiralcel OD-H, hexane (hexane)/2-propanol (2-propanol) ═ 90/10, v ═ 1.0ml · min^-1,λ＝254nm,t(major)＝19.86min,t(minor)＝34.51min]；[α]_D ²⁸-6.5(c1.00,CH₂Cl₂).

Effect example 3

After compounds Ia to Ik, compounds IIa to IIu, compounds IIIa to IIIf, compounds IVa to IVi, compounds Va to Vg and compounds VIa to VIe were placed in the air for 6 months, respectively, the catalytic action of the metal iridium complexes represented by general formulae I to VI of the present invention was determined with reference to the methods for producing the compounds represented by formula P in Effect example 1 and Effect example 2.

TABLE 9

Compound (I)

Catalyst and process for preparing same

Yield of

ee value (%)

Numbering

Catalyst and process for preparing same

Yield of

ee value (%)

P1

Ia

81

92

P12

IVc

95

93

P2	Ib	77	92	P14	IIIa	87	98
								P3	Ik	78	92	P16	IIIb	84	98
P4	Vg	84	89	P18	IIIe	79	98
								P8	IIh	75	91	P23	IIIf	74	98
P10	IIk	77	90	/	/	/	/

Comparative example 1

To a Schlenk tube, under protection of argon, substrate S1(75.6mg,0.2mmol), 7a (6.6mg,0.01mmol,5 mol%) and DBU (3.0mg,0.02mmol) were added in 2.0mL of dichloromethane (CH)₂Cl₂) The reaction was stirred at room temperature for 24 hours, and no target product was formed by TLC.

Comparative example 2

To a Schlenk tube, under protection of argon, substrate S1(75.6mg,0.2mmol), 7b (7.6mg,0.01mmol,5 mol%) and DBU (3.0mg,0.02mmol) were added in 2.0mL of dichloromethane (CH)₂Cl₂) The reaction was stirred at room temperature for 24 hours, and no target product was formed by TLC.

Claims

1. A metal iridium complex represented by a general formula I, a general formula II, a general formula III, a general formula IV, a general formula V or a general formula VI, wherein carbon marked by x is chiral carbon or achiral carbon, and when the carbon is chiral carbon, the chiral carbon is in an S configuration or an R configuration;

wherein R is¹、R^1a、R^1b、R^1c、R^1dAnd R^1eIndependently is C₃-C₆Cycloalkyl, substituted or unsubstituted C₆-C₂₀Aryl of (a);

R²、R^2’、R^2a、R^2a’、R^2b、R^2b’、R^2cand R^2c’Independently of one another is hydrogen, C₁-C₈Alkyl, substituted or unsubstituted C₆An aryl group; or R²And R^2’And the carbon atoms to which they are attached together form C₅-C₈Cycloalkyl groups of (a);

R³is composed ofWherein R is_aIs C₁-C₈Perfluoroalkyl group of (1), substituted or unsubstituted C₆Aryl of (a); r_bIs C₁-C₈Alkyl of (C)₁-C₈Alkoxy group of (C)₁-C₈A perfluoroalkyl group of (a);

R⁴、R^4aand R^4bIndependently of one another is hydrogen, C₁-C₈Alkyl orWherein R is_c、R_c' or R_c"independently is C₁-C₈Alkyl groups of (a);

R⁵hydrogen, halogen;

wherein, said substituted C₆-C₂₀Said substitution in aryl means substitution with one or more of the following substituents: c₁-C₁₆Hydrocarbyloxy group of (C)₁-C₁₆Alkyl of (C)₁-C₁₆When a plurality of substituents are present, the substituents may be the same or different.

2. The metallic iridium complex of formula I, formula II, formula III, formula IV, formula V or formula VI as claimed in claim 1,

when said substituted C₆-C₂₀Said substitution in aryl of (A) is by C₁-C₁₆When substituted by alkoxy of (A), said C₁-C₁₆The alkoxy of (A) is methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy;

and/or, when said substituent is C₁-C₁₆When there is an alkyl group, said C₁-C₁₆The alkyl group of (a) is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl;

and/or, when said substituted C₆-C₂₀Said substitution in aryl of (A) is by C₁-C₁₆When substituted with fluoroalkyl, said C₁-C₁₆By fluoroalkyl is meant C substituted by one or more fluorine atoms₁-C₁₆A fluoroalkyl group of (a); said C₁-C₁₆The fluoroalkyl group of (a) is trifluoromethyl.

3. The metallic iridium complex of formula I, formula II, formula III, formula IV, formula V or formula VI as claimed in claim 1,

R²、R²’、R^2a、R^2a’、R^2b、R^2b’、R^2c、R^2c’、R_b、R⁴、R^4a、R^4b、R_c、R_c’、R_c", said C₁-C₈The alkyl group of (a) is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl;

and/or, R¹、R^1a、R^1b、R^1c、R^1d、R^1eWherein C is₃-C₆The cycloalkyl group of (a) is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;

and/or, R_a、R_bWherein C is₁-C₈Is perfluoroalkyl of Wherein, including the respective isomeric forms;

and/or, R¹、R^1a、R^1b、R^1c、R^1d、R^1e、R²、R²’、R^2a、R^2a’、R^2b、R^2b’、R^2c、R^2c’、R_aAnd said substituted or unsubstituted C₆-C₂₀Aryl of (a) is substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 9-anthracenyl, or substituted or unsubstituted 9-phenanthrenyl; said substituted phenyl is

And/or, R_b、X¹、X^1a、X^1b、X^1c、X^1dAnd X^1eIn (b), the C₁-C₈Alkoxy of (a) is methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy;

and/or, X¹、X^1a、X^1b、X^1c、X^1dAnd X^1eWherein said halogen is fluorine, chlorine, bromine or iodine;

and/or when R²And R^2’And the carbon atoms to which they are attached together form C₅-C₈In the case of a cycloalkyl group of (A), said C₅-C₈The cycloalkyl group of (a) is cyclopentyl or cyclohexyl.

4. The iridium metal complex of formula II, formula III, formula IV or formula V according to claim 1,

R³in (1), the

And/or, R³In (1), the

And/or, R⁴In (1), the

5. The metallic iridium complex of formula I, formula II, formula III, formula IV, formula V or formula VI as claimed in claim 1,

in the metal-based complex of the general formula I, R¹Is C₃-C₆Cycloalkyl or substituted or unsubstituted C₆-C₂₀Aryl of (a); x¹Is halogen or C₁-C₈Alkoxy group of (a);

and/or, in the metal complex of the formula II, R^1aIs C₃-C₆Cycloalkyl or substituted or unsubstituted C₆-C₂₀Aryl of (a); r²And R^2’Independently is substituted or unsubstituted C₆Aryl of (a); or R²And R^2’And the carbon atoms to which they are attached together form C₅-C₈Cycloalkyl groups of (a); r³Is composed ofWherein R is_aIs C₁-C₈Perfluoroalkyl group of (1), substituted or unsubstituted C₆Aryl of (a); r_bIs C₁-C₈Alkyl of (C)₁-C₈Alkoxy group of (C)₁-C₈A perfluoroalkyl group of (a); x^1aIs halogen or C₁-C₈Alkoxy group of (a);

and/or, in the metal complex of the formula III, R^1bIs substituted or unsubstituted C₆Aryl of (a); r^2a、R^2a’And R⁴Independently is C₁-C₈Alkyl groups of (a); x^1bIs halogen;

and/or, in the metal complex of the formula IV, R^1cIs substituted or unsubstituted C₆Aryl of (a); r^2bAnd R^2b’Independently is C₁-C₈Alkyl, substituted or unsubstituted C₆Aryl of (a); r^4aIndependently is C₁-C₈Alkyl orWherein R is_c、R_c' and R_c"independently is C₁-C₈Alkyl groups of (a); r⁵Is hydrogen or halogen; x^1cIs halogen or C₁-C₈Alkoxy group of (a);

and/or, in the metal complex of the formula V, R^1dIs substituted or unsubstituted C₆Aryl of (a); r^2c、R^2c’And R^4bIndependently of one another is hydrogen, C₁-C₈Alkyl, substituted or unsubstituted C₆Aryl of (a); x^1dIs halogen or C₁-C₈Alkoxy group of (a);

and/or, in the metal complex of the formula VI, R^1eIs substituted or unsubstituted C₆Aryl of (a); x^1eIs halogen or C₁-C₈Alkoxy group of (2).

6. The iridium metal complex of claim 1, wherein the iridium metal complex of formula I is any one of the following compounds:

a metal-based complex represented by the general formula II, which is any one of the following compounds:

a metal-based complex represented by the general formula III, which is any one of the following compounds:

a metal-based complex of formula IV, which is any one of the following compounds:

a metal-based complex represented by formula V, which is any one of the following compounds:

a metal-based complex of formula VI, which is of any of the following structures:

7. a metal iridium complex IIIa single crystal characterized in that, in a single crystal X-ray diffraction spectrum using a radiation source Cu-K α, the crystal is monoclinic, space group is P21, and unit cell parameters thereof are as follows: α -90 °, β -92.5300 (10 °), γ -90 °, unit cell volumeThe number of asymmetric units in the unit cell, Z, is 2;

8. the method for producing a single crystal of the metal iridium complex IIIa according to claim 7, comprising the steps of: and (3) mixing the metal iridium complex IIIa and a benign solvent, then dropwise adding the poor solvent until turbidity just appears, dropwise adding the benign solvent, and standing.

9. A method for preparing the iridium metal complex of formula I, formula II, formula III, formula IV, formula V or formula VI as claimed in any of claims 1 to 6, comprising the steps of: in an organic solvent, in the presence of alkali, a compound shown as a formula a and [ Ir (cod) X¹]₂A compound represented by the formula b and [ Ir (cod) X^1a]₂A compound represented by the formula c and [ Ir (cod) X^1b]₂A compound represented by the formula d and [ Ir (cod) X^1c]₂A compound represented by the formula e and [ Ir (cod) X^1d]₂Or a compound of formula f with [ Ir (cod) X^1e]₂Carrying out a complexation reaction as shown below; respectively preparing metal iridium complexes shown in a general formula I, a general formula II, a general formula III, a general formula IV, a general formula V or a general formula VI;

wherein, the symbols, the groups are defined as in any one of claims 1 to 6; y is halogen, CF₃SO₃、OTf、BF₄Or ClO₄。

10. The method according to claim 9, wherein the organic solvent is one or more of an aromatic hydrocarbon solvent, a halogenated hydrocarbon solvent, an ether solvent, an amide solvent, an alkane solvent and a nitrile solvent; the aromatic hydrocarbon solvent is preferably one or more of benzene, toluene and xylene; the halogenated hydrocarbon solvent is preferably one or more of carbon tetrachloride, dichloromethane and trichloromethane; the ether solvent is preferably one or more of tetrahydrofuran, diethyl ether and 1, 4-dioxane; the amide solvent is preferably N, N-dimethylformamide; the alkane solvent is preferably one or more of cyclohexane, n-pentane, n-hexane and n-heptane; the nitrile solvent is preferably acetonitrile;

and/or the base is an inorganic base or an organic base, and the inorganic base is preferably one or more of sodium carbonate, potassium carbonate, cesium carbonate, potassium phosphate, sodium hydride, sodium methoxide, sodium ethoxide, sodium acetate, potassium tert-butoxide, sodium tert-butoxide and lithium tert-butoxide; the organic base is preferably one or more of triethylamine, piperidine, pyridine, N-lutidine and 2, 6-lutidine;

and/or, said [ Ir (cod) X¹]₂And a compound shown as a formula [ Ir (cod) X^1a]₂And a compound represented by the formula b, [ Ir (cod) X^1b]₂And a compound represented by the formula c, [ Ir (cod) X^1c]₂And a compound represented by the formula d, [ Ir (cod) X^1d]₂And a compound represented by the formula e or [ Ir (cod) X^1e]₂The mol ratio of the compound to the compound shown as the formula f is 1:1-1: 3.5; preferably 1:2 to 1: 3.5;

and/or, said [ Ir (cod) X¹]₂、[Ir(cod)X^1a]₂、[Ir(cod)X^1b]₂、[Ir(cod)X^1c]₂、[Ir(cod)X^1d]₂Or [ Ir (cod) X^1e]₂The molar ratio of the alkali to the alkali is 1:1-1: 20; preferably 2:15 to 1: 20;

and/or the organic solvent is reacted with [ Ir (cod) X¹]₂、[Ir(cod)X^1a]₂、[Ir(cod)X^1b]₂、[Ir(cod)X^1c]₂、[Ir(cod)X^1d]₂Or [ Ir (cod) X^1e]₂The volume-mass ratio of (A) is 0.1mL/mg to 1 mL/mg;

and/or the temperature of the complexation reaction is 0-150 ℃; preferably 25 ℃ to 125 ℃;

and/or the time of the complexation reaction is 24-48 hours.

11. Use of the iridium metal complex of formula I, formula II, formula III, formula IV, formula V or formula VI as claimed in any of claims 1 to 6 as a catalyst in asymmetric allyl substitution reactions.

12. The use of claim 11, wherein said asymmetric allylic substitution reaction comprises the steps of: in an organic solvent, under the action of alkali, and under the catalysis of one or more of the metal iridium complexes shown in the general formula I, the general formula II, the general formula III, the general formula IV, the general formula V or the general formula VI in any one of claims 1 to 6, carrying out asymmetric allyl substitution reaction shown in the following formula S1 on the compound shown in the formula S1 to prepare a benzindole compound shown in the formula P; wherein, the carbon marked by the letter is chiral carbon or non-chiral carbon, and when the carbon is chiral carbon, the chiral carbon is in S configuration or R configuration;

in the compound shown as the formula S1 and the compound shown as the formula P, R_a1Is mono-or polysubstituted, the same or different, selected from one or more of the following substituents: halogen, substituted or unsubstituted C₁-C₄Or substituted or unsubstituted C₁-C₄Alkoxy group of (a); r_b1Is substituted or unsubstituted C₁-C₄Or substituted or unsubstituted C₂-C₄Alkenyl of (a); r_c1Is composed ofWherein M is NH or O; r_d1Is C₁-C₄Alkyl, C substituted by one or more halogens₁-C₄Alkyl or C₁-C₄Alkoxy group of (a); r_e1Is C₁-C₄Alkyl or C₆-C₂₀An aryl group; r_a1And R_b1In (b), said substituted C₁-C₄Alkyl of (2) or said substituted C₁-C₄The substituent in the alkoxy group of (a) means a substituent substituted with one or more of the following substituents: halogen, C₁-C₄Alkoxy group of (C)₁-C₄Alkyl of (C)₆～C₂₀Aryl radicals, or substituted by one or more C₁-C₄Alkoxy-substituted C₆-C₂₀And when the substituent is a plurality of the aryl groups, the substituents are the same or different.

13. The use according to claim 12,

when said substituted C₁-C₄Alkyl of (2) or said substituted C₁-C₄When said substitution in said alkoxy group of (a) is by halogen, said halogen is F, Cl, Br or I;

when said substituted C₁-C₄Alkyl of (2) or said substituted C₁-C₄Said substitution in alkoxy of (A) is by C₁-C₄When substituted by alkoxy of (A), said C₁-C₄Alkoxy of (a) is methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy;

when said substituted C₁-C₄Alkyl of (2) or said substituted C₁-C₄Said substitution in alkoxy of (A) is by C₁-C₄When substituted with an alkyl group of (A), said C₁-C₄The alkyl group of (a) is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl;

when said substituted C₁-C₄Alkyl of (2) or said substituted C₁-C₄Said substitution in alkoxy of (a) is by C₆～C₂₀When aryl is substituted, said C₆～C₂₀Aryl is phenyl;

when said substituted C₁-C₄Alkyl of (2) or said substituted C₁-C₄Said substitution in alkoxy of (a) is by one or more C₁-C₄Alkoxy-substituted C₆-C₂₀When substituted by aryl, said group is substituted by one or more C₁-C₄Alkoxy-substituted C₆-C₂₀Aryl is p-methoxyphenyl.

14. The use according to claim 12,

R_a1wherein the halogen is F, Cl, Br or I;

and/or, R_a1Wherein said substituted or unsubstituted C₁-C₄The alkyl group of (a) is a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted n-propyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted n-butyl group, a substituted or unsubstituted isobutyl group, or a substituted or unsubstituted tert-butyl group; the substituted methyl is benzyl or p-methoxybenzyl;

and/or, R_a1Wherein said substituted or unsubstituted C₁-C₄The alkoxy group of (a) is a substituted or unsubstituted methoxy group, a substituted or unsubstituted ethoxy group, a substituted or unsubstituted n-propoxy group, a substituted or unsubstituted isopropoxy group, a substituted or unsubstituted n-butoxy group, a substituted or unsubstituted isobutoxy group, or a substituted or unsubstituted tert-butoxy group;

and/or, R_b1In (b), the C₂-C₄The alkenyl group of (A) is ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl or 3-butenyl;

and/or, R_d1Or R_e1In (b), the C₁-C₄The alkyl group of (a) is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl;

and/or, R_d1Wherein said C is substituted by one or more halogens₁-C₄The halogen in the alkyl group of (a) means fluorine, chlorine, bromine or iodine; said C substituted by one or more halogens₁-C₄C in the alkyl group of (1)₁-C₄The alkyl group of (a) is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl; said C substituted by one or more halogens₁-C₄The alkyl group of (A) is preferably

And/or, R_d1In (b), the C₁-C₄Alkoxy of (a) is methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy;

and/or, R_e1In (1), theC₆-C₂₀Aryl is phenyl.

15. The use according to claim 12, wherein in the asymmetric allyl substitution reaction, the organic solvent is one or more of an aromatic hydrocarbon solvent, a halogenated hydrocarbon solvent, an ether solvent, an amide solvent, an alkane solvent and a nitrile solvent; the aromatic hydrocarbon solvent is preferably toluene; the halogenated hydrocarbon solvent is preferably dichloromethane and/or trichloromethane; the ether solvent is preferably one or more of tetrahydrofuran, diethyl ether and 1, 4-dioxane; the alkane solvent is preferably n-hexane; the nitrile solvent is preferably acetonitrile;

and/or the base is an organic base and/or an inorganic base, the organic base preferably being 1, 8-diazabicycloundecen-7-ene, N-diisopropylethylamine, triethylamine and 1, 4-diazabicyclo [2.2.2]One or more of octane; the inorganic base is preferably Cs₂CO₃、K₂CO₃、Na₂CO₃、Li₂CO₃One or more of lithium tert-butoxide, sodium tert-butoxide and potassium tert-butoxide.