CN105854947A - Chiral pyridine biimidazole ligand transition metal complex catalyst and preparation method thereof - Google Patents

Abstract

The invention relates to a chiral pyridine bis-imidazole ligand transition metal complex catalyst and a preparation method thereof. The general structural formula of this compound is: Among them: M is a transition metal; R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ are hydrogen atoms, C1-C30 alkane groups or C6-C30 aryl groups ; X is a halogen atom or a halide metal salt ion; * means racemization or chirality, and when it is "chiral", it means R configuration or S configuration. The chiral pyridine bis-imidazole ligand used in the present invention can be modified by functional groups to change the electronic properties and steric hindrance of the ligand, and has moderate catalytic activity and stereoselectivity as a catalyst precursor for the asymmetric hydroboration of alkenyl boranes sex. The preparation method of the present invention is simple, the raw material is cheap and easy to obtain, is friendly to the environment, the reaction condition is mild, the yield is high, and the synthesis operation is simple and convenient.

Description

Chiral pyridine bis-imidazole ligand transition metal complex catalyst and preparation method thereof

technical field

The invention relates to a chiral pyridine bis-imidazole ligand transition metal complex catalyst and a preparation method thereof.

Background technique

Due to the advantages of high efficiency and low consumption, transition metal catalysts have attracted widespread attention of scientific researchers. However, in the field of homogeneous catalysis, noble metal catalytic systems are still dominant. Precious metals have limited reserves, are expensive, and are toxic to heavy metals. In contrast, cheap metals are abundant and environmentally friendly. Therefore, it is of great practical value to develop new cheap metal catalysts to replace noble metal catalysts in transition metal catalyzed reactions. In the past ten years, the use of cheap metal catalysts in homogeneous catalytic reactions has been widely developed.

Ligands play a vital role in transition metal-catalyzed reactions, and the efficiency and selectivity of reactions can be improved by modifying the ligand structure. The Pincer ligand was first reported by Shaw's research group in 1970 (Moulton, C. J.; Shaw, B. L., J. Chem. Soc., Dalton Trans. 1976, 1020.). This type of ligand structure is highly adjustable, and the transition metal complex coordinated with the pincer ligand has good thermal stability, so it has been rapidly developed in the field of transition metal catalysis. The chiral pyridine bisoxazoline (Pybox) ligand is also a pincer-type ligand, which was first reported by Itoh's research group (Nishiyama, H.; Itoh, K., Organometallics1989, 8, 846.). Pybox ligands are easy to prepare, and have been widely used in asymmetric synthesis reactions, and some of them have been commercialized. In contrast, chiral pyridine bis-imidazole ligands with similar structures to Pybox ligands have rarely been used in catalytic reactions. To the best of our knowledge, complexes of chiral pyridine bis-imidazole ligands coordinated with inexpensive metals such as iron and cobalt have not been reported so far. Therefore, it is of great research value to synthesize cheap metal catalysts with chiral pyridine biimidazole coordination and to explore their application in asymmetric synthesis reactions.

1,1-Diboryl compounds are an important class of organic synthesis intermediates, which can construct complex organic molecules through nucleophilic substitution reactions or Suzuki-Miyaura cross-coupling reactions. The Shibata group reported that diboryl compounds reacted with 2,2,6,6-tetramethylpiperidinium lithium (LTMP) at lower temperatures to form stable carbanions, and then reacted with ketones to form tetrasubstituted alkenes (Endo , K.; Shibata, T., Chem. Lett.2011, 40, 1440). The Morken research group recently reported that under the action of sodium tert-butoxide, 1,1-diboryl compounds and halogenated hydrocarbons react to achieve alkylation to obtain non-terminal borate esters (Hong, K.; Morken, J. P., J . Am. Chem. Soc. 2014, 136, 10581). In the Suzuki-Miyaura cross-coupling reaction, the Shibata group found that di-tert-butylphosphine palladium is used as a catalyst, potassium hydroxide is used as a base, and diboryl compounds can be efficiently converted into coupling products at room temperature (Endo, K.; Shibata, T., J. Am. Chem. Soc. 2010, 132, 11033). The Morken research group found that palladium acetate and TADDOL-derived monophosphine ligands as catalyst precursors can promote the coupling reaction of diboryl compounds and aryl halohydrocarbons, and obtain very high enantioselectivity (Sun, C .; Morken, J. P., J. Am. Chem. Soc. 2014, 136, 6534). Chiral 1,1-diboryl compounds can be transformed into other valuable chiral molecules under the induction of achiral catalysts, so these compounds have important application value. Hall's group found that palladium acetate and XPhos were used as catalyst precursors to convert chiral 1,1-diboryl compounds into chiral alkyl boron species through Suzuki-Miyaura cross-coupling reactions, and then through further coupling the alkyl Boron species are transformed into complex organic molecules (Lee, J.; Hall, D. G. Nat. Chem. 2011, 3,894). But there are only two reports on the synthesis of chiral 1,1-diboryl compounds. The first case was reported by Hall’s research group. The reaction uses cuprous chloride and a ferrocene skeleton with a large sterically hindered chiral bisphosphine ligand as a catalyst precursor, and the substrate is limited to alkenyl borane conjugated with an ester group. (Lee, J.; Hall, D. G. Nat. Chem. 2011, 3, 894); the second case was reported by Yun's research group, which uses cuprous chloride and a large hindered chiral bisphosphine ligand (R )-dtbm-segphos catalysis, the system has excellent catalytic activity and selectivity for linear alkenyl borane and aromatic cycloalkenyl borane (Feng, X.; YunJ., Angew. Chem., Int. Ed ., 2013, 52, 3989). There are no reports about other metal complexes catalyzing this type of reaction, and the ligands used by Hall's and Yun's groups are expensive and difficult to synthesize. It is of great significance to develop cheap metal catalysts with chiral pyridine biimidazole coordination to realize this reaction.

Contents of the invention

One of the objectives of the present invention is to provide a class of chiral pyridine diimidazole ligand transition metal complex catalysts.

The second object of the present invention is to provide a preparation method of the catalyst.

To achieve the above object, the present invention adopts following reaction mechanism:

.

A chiral pyridine bis-imidazole ligand transition metal complex catalyst is characterized in that the structural formula of the catalyst is:

General structural formula:

Among them: M is a transition metal; R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ are hydrogen atoms, C1-C30 alkane groups or C6-C30 aryl groups ; X is a halogen atom or a halide metal salt ion; * means racemization or chirality, and when it is "chiral", it means R configuration or S configuration.

The aforementioned M is iron or cobalt.

The aforementioned X is: chlorine atom, bromine atom, iodine atom, cobalt tetrachloride ion, cobalt tetrabromide ion, cobalt tetraiodide ion, ferric tetrachloride ion, ferric tetrabromide ion or ferric tetraiodide ion.

The aforementioned R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , and R ⁹ are independently hydrogen, C1-C6 alkyl, or C6-C12 aryl.

The aforementioned C1-C6 alkyl groups are methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl.

The above-mentioned C6-C12 aryl group is: phenyl, 2, 4, 6-trimethylphenyl or 2,6-diisopropylphenyl.

A method for preparing the above-mentioned chiral pyridine bis-imidazole ligand transition metal complex catalyst, characterized in that the specific steps of the method are: under an inert atmosphere, at 20-30 ° C, the chiral pyridine bis-imidazole ligand The tetrahydrofuran solution of MX2 was added dropwise in the tetrahydrofuran solution of MX ₂ ; stirred for 12 h; the reaction was completed, filtered, and the filter cake was washed with ether to obtain a chiral pyridine bis-imidazole coordination transition metal complex catalyst; the chiral pyridine bis The molar ratio of imidazole ligand to MX ₂ is 1:1-1:2.

The molar concentration of the aforementioned MX ₂ solution in tetrahydrofuran is 0.01 mol/liter to 0.1 mol/liter.

The molar concentration of the tetrahydrofuran solution of the chiral pyridine bis-imidazole ligand is 0.1 mol/liter to 1 mol/liter.

The chiral pyridine bis-imidazole ligand-metal complex 1 described in the present invention can be , , , or

An application of the chiral pyridine bis-imidazole ligand-iron, cobalt complex catalyst is used as a catalyst precursor for the asymmetric hydroboration reaction of alkenyl borane.

As a preferred solution, the asymmetric hydroboration reaction of alkenyl borane refers to an asymmetric hydroboration reaction that only occurs at the α-position double bond.

As a further preferred version, the hydroboration reaction of alkenyl borane refers to the use of the chiral pyridine bis-imidazole ligand-iron, cobalt complex as a catalyst precursor, pinacol borane (HBpin) As a boron reagent, in the presence of NaBEt ₃ H, an asymmetric hydroboration reaction occurs to generate 1,1-bisborane-substituted hydrocarbon derivatives.

As a further preferred version, the asymmetric hydroboration reaction includes the following operations:

First, in the glove box, chiral pyridine bis-imidazole ligand-iron or cobalt complex and solvent are added into the reaction vial to obtain a purple-black or orange-yellow catalyst precursor solution. Next, alkenyl borane and pinacol borane (HBpin) were added to the reaction vial, and then the catalyst activator NaBEt ₃ H was added to the above reaction vial. After the reaction was stirred at room temperature for 10-18 hours, it was quenched by exposure to air. Then the above reaction solution was transferred to a round bottom bottle, the solvent was removed by rotary evaporation, and the asymmetric hydroboration product was obtained by flash column chromatography.

As a further preferred version, the molar ratio of alkenyl borane and pinacol borane with α-position double bonds is 1:1, and the chiral pyridine bis-imidazole ligand-iron, cobalt complex and pinacol borane The molar ratio of alcohol borane is 0.02:1～0.04:1, and the molar ratio of NaBEt ₃ H to the pyridine bis-imidazole ligand-cobalt complex is 3:1; the organic solvent is selected from tetrahydrofuran, toluene , any one of n-hexane and ether.

Alkenyl borane described in the present invention can be as follows general formula: or Represents that R in the general formula represents any alkyl group; Ar in the general formula represents ^an aryl group or an aryl group with substituents such as an alkyl group, an alkoxy group, or a halogen atom.

The chiral pyridine bis-imidazole ligand used in the present invention can be modified by functional groups to change the electronic properties and steric hindrance of the ligand.

The preparation method of the chiral pyridine bis-imidazole ligand-iron and cobalt complex provided by the invention is simple, the raw materials are cheap and easy to obtain, the environment is friendly, the reaction conditions are mild, the yield is high, and the synthesis operation is simple.

The chiral pyridine bis-imidazole ligand-iron and cobalt complex of the present invention is an ionic complex and used as a catalyst precursor has moderate catalytic activity and stereoselectivity for the asymmetric hydroboration of alkenyl borane.

Description of drawings

Fig. 1 is a schematic diagram of the single crystal structure of [(NNN) ₂ Fe] ²⁺ Cl ₂ ^2- (complex 1a) obtained in Example 1 of the present invention.

Fig. 2 is a schematic diagram of the single crystal structure of [(NNN) ₂ Co] ²⁺ Cl ₂ ^2- (complex 1d) obtained in Example 4 of the present invention.

Fig. 3 is a schematic diagram of the single crystal structure of [(NNN) ₂ Co] ²⁺ CoCl ₄ ^2- (complex 1f) obtained in Example 5 of the present invention.

detailed description

Below in conjunction with embodiment the present invention is described in further detail and completely. The chiral pyridine bis-imidazole ligand used in the examples was prepared according to the method described in the reference document Org. Lett. 2005, 7, 3393.

Embodiment 1: prepare chiral pyridine bis-imidazole ligand-iron complex 1a of the present invention, its structural formula is:

In the glove box, FeCl ₂ (126.8 mg, 1.0 mmol, 1.0 equiv) and THF (50 mL) were added to a 100 mL schlenk tube, and then chiral pyridine bis-imidazole ligand (1.04 g, 2.0 mmol, 2.0 equiv ) THF solution (10 mL) was added dropwise to the above solution, and at the moment of addition, the color of the reaction solution rapidly changed to purple-black, and a purple-black solid was precipitated. After the reaction was stirred at room temperature for 24 h, it was filtered, washed with THF and ether, and the solvent was drained to obtain a purple-black powder (1.02 g, 87%). Then put the above powder (15 mg) into a sample bottle with a volume of 4 mL, dissolve it in DMSO (1 mL), transfer the above sample bottle to a sample bottle with a volume of 18 mL containing ether solvent, and the ether solvent cannot cover Put the small sample bottle in the mouth, let it stand for several days, wait for the ether to slowly diffuse into the DMSO solution of the complex, and get black crystals, which are used for single crystal diffraction, and some of the bond lengths (Å) and bond angles ( ^o ) are: Fe(1)-N(2), 2.005(7); Fe(1)-N(1), 1.905(7); Fe(1)-N(3), 1.979(7); Fe(1)- N(6), 2.024(7); Fe(1)-N(4), 1.908(7); Fe(1)-N(5), 1.999(7); N(2)-Fe(1)- N(6), 89.2(3); N(1)-Fe(1)-N(2), 79.4(3); N(1)-Fe(1)-N(3),79.3(3); N(1)-Fe(1)-N(6), 101.2(3); N(1)-Fe(1)-N(4), 178.7(3); N(1)-Fe(1)- N(4), 100.8(3); N(3)-Fe(1)-N(2), 158.6(3); N(3)-Fe(1)-N(6), 97.2(3); N(3)-Fe(1)-N(5), 86.2(3); N(4)-Fe(1)-N(2), 101.9(3); N(4)-Fe(1)- N(3), 99.3(3); N(4)-Fe(1)-N(6), 78.9(3); N(4)-Fe(1)-N(5), 79.0(3); N(5)-Fe(1)-N(2), 95.5(3); N(5)-Fe(1)-N(6), 158.0(3).Anal. Calcd for C ₇₀ H ₅₈ Cl ₂ FeN ₁₀ : C,72.10; H, 5.01; N,12.01. Found: C,72.21; H, 5.32; N, 12.64.

Example 2: Preparation of chiral pyridine bis-imidazole ligand-iron complex [(NNN) ₂ Fe] ²⁺ FeCl ₄ ^2- (complex 1b) according to the present invention, its structural formula is:

In the glove box, FeCl ₂ (126.8 mg, 1.0 mmol, 1.0 equiv) and THF (50 mL) were added to a 100 mL schlenk tube, and then the chiral pyridine bis-imidazole ligand (575.7 mg, 1.0 mmol, 1.0 equiv ) THF solution (10 mL) was added dropwise to the above solution, and at the moment of addition, the color of the reaction solution rapidly changed to purple-black, and a purple-black solid was precipitated. After the reaction was stirred at room temperature for 24 h, it was filtered, washed with THF and ether, and the solvent was drained to obtain a purple-black powder (583.1 mg, 83%). Anal. Calcd for C ₇₈ H ₇₄ Cl ₄ Fe ₂ N ₁₀ : C, 66.68; H, 5.31; N, 9.97. Found: C, 67.06; H, 5.68; N, 10.26.

Example 3: Preparation of chiral pyridine bis-imidazole ligand-iron complex [(NNN) ₂ Fe] ²⁺ Cl ₂ ^2- (complex 1c) according to the present invention, its structural formula is:

In the glove box, FeCl ₂ (126.8 mg, 1.0 mmol, 1.0 equiv) and THF (50 mL) were added to a 100 mL schlenk tube, and then chiral pyridine bis-imidazole ligand (1.11 g, 2.0 mmol, 2.0 equiv ) THF solution (10 mL) was added dropwise to the above solution, the color of the reaction solution rapidly changed to purple-black, and a purple-black solid was precipitated. After the reaction was stirred at room temperature for 24 h, it was filtered, washed with THF and ether, and the solvent was drained to obtain a purple-black powder (1.00 g, 81%). Anal. Calcd for C ₇₀ H ₅₆ Cl ₄ FeN ₁₀ : C, 68.08; H, 4.57; N, 11.54. Found: C, 68.53; H, 4.91; N, 11.70.

Example 4: Preparation of chiral pyridine bis-imidazole ligand-cobalt complex [(NNN) ₂ Co] ²⁺ Cl ₂ ^2- (complex 1d) according to the present invention, its structural formula is:

In the glove box, CoCl ₂ (129.8 mg, 1.0 mmol, 1.0 equiv) and THF (50 mL) were added to a 100 mL schlenk tube, and then the chiral pyridine bis-imidazole ligand (1.04 g, 2.0 mmol, 2.0 equiv ) THF solution (10 mL) was added dropwise to the above solution, the color of the reaction solution rapidly changed to orange, and an orange solid was precipitated. After the reaction was stirred at room temperature for 24 h, it was filtered, washed with THF and ether, and the solvent was drained to obtain an orange-yellow powder (970.3 mg, 83%). Then put the above powder (15 mg) into a 4 mL sample bottle, dissolve it in DMSO (1 mL), transfer the above sample bottle to a 18 mL sample bottle containing ether solvent, and the ether solvent should not be covered Small sample bottle mouth, let it stand for several days, wait for the ether to slowly diffuse into the DMSO solution of the complex, and obtain orange crystals, which are used for single crystal diffraction, and some of the bond lengths (Å) and bond angles ( ^o ) are : Co(1)-N(1), 2.063(6); Co(1)-N(2), 2.133(7); Co(1)-N(3), 2.141(8); Co(1) -N(6), 2.063(7); Co(1)-N(7), 2.135(7); Co(1)-N(8), 2.120(7); N(1)-Co(1) -N(2), 75.7(3); N(1)-Co(1)-N(3), 75.7(3); N(1)-Co(1)-N(5), 103.0(3) ; N(1)-Co(1)-N(6), 105.8(3); N(2)-Co(1)-N(3), 151.0(3); N(2)-Co(1) -N(5), 90.3(3); N(4)-Co(1)-N(1), 178.7(3); N(4)-Co(1)-N(2), 104.4(3) ; N(4)-Co(1)-N(3), 104.4(3); N(4)-Co(1)-N(5), 75.7(3); N(4)-Co(1) -N(6), 75.5(3); N(5)-Co(1)-N(3), 100.4(3); N(6)-Co(1)-N(2), 97.3(3) ; N(6)-Co(1)-N(3), 86.3(3); N(6)-Co(1)-N(5), 151.2(3). Anal. Calcd for C ₇₀ H ₅₈ Cl ₂ CoN ₁₀ : C,71.91; H, 5.00; N, 11.98. Found: C,72.17; H, 5.04; N, 11.91.

Example 5: Preparation of chiral pyridine bis-imidazole ligand-cobalt complex [(NNN) ₂ Co] ²⁺ CoCl ₄ ^2- (complex 1f) according to the present invention, its structural formula is:

In the glove box, CoCl ₂ (129.8 mg, 1.0 mmol, 1.0 equiv) and THF (50 mL) were added to a 100 mL schlenk tube, and then chiral pyridine bis-imidazole ligand (575.7 mg, 1.0 mmol, 1.0 equiv ) THF solution (10 mL) was added dropwise to the above solution, the color of the reaction solution rapidly changed to orange-yellow, and an orange-yellow solid was precipitated. After the reaction was stirred at room temperature for 24 h, it was filtered, washed with THF and ether, and the solvent was drained to obtain an orange-yellow powder (578.3 mg, 82%). Then put the above powder (15 mg) into a sample bottle with a volume of 4 mL, dissolve it in DMSO (1 mL), transfer the above sample bottle to a sample bottle with a volume of 18 mL containing ether solvent, and the ether solvent cannot cover Small sample bottle mouth, let it stand for several days, wait for the ether to slowly diffuse into the DMSO solution of the complex, and obtain orange crystals, which are used for single crystal diffraction, and some of the bond lengths (Å) and bond angles ( ^o ) are : Co(1)-N(1), 2.086(6); Co(1)-N(2), 2.114(7); Co(1)-N(3),2.035(7); Co(1) -N(4), 2.052(6); Co(1)-N(5), 2.144(6); Co(1)-N(6), 2.102(6); N(1)-Co(1) -N(2), 75.5(3); N(1)-Co(1)-N(5), 103.1(2); N(1)-Co(1)-N(6), 104.0(2) ; N(2)-Co(1)-N(5), 85.3(3); N(3)-Co(1)-N(1), 75.9(3); N(3)-Co(1) -N(2),151.4(2); N(3)-Co(1)-N(4), 101.1(3); N(3)-Co(1)-N(5), 102.5(2) ; N(3)-Co(1)-N(6), 88.7(2); N(4)-Co(1)-N(1), 176.8(3); N(4)-Co(1) -N(2), 107.5(3); N(4)-Co(1)-N(5), 76.2(3); N(4)-Co(1)-N(6), 76.9(3) ; N(6)-Co(1)-N(2), 96.9(2); N(6)-Co(1)-N(5), 152.5(2). Anal. Calcd for C ₇₈ H ₇₄ Cl ₄ Co ₂ N ₁₀ : C, 66.39; H, 5.29; N,9.93. Found: C, 66.28; H, 5.31; N, 10.33.

Embodiment 6: the catalytic activity experiment of complex 1 described in embodiment 1 to the asymmetric hydroboration reaction of styryl borane

Taking catalyst precursor 1f as an example in the asymmetric hydroboration of styryl-2,3-dihydro-1hydro-naphthalene[1,8-de][1,3,2]oxadiazoleboron: first in the glove box Inside, complex 1f (4.2 mg, 0.003 mmol) and THF (5 mL) were added to the reaction vial and stirred well. Then styrylborane (40.5 mg, 0.15 mmol), HBpin (22.5 μL, 0.15 mmol) and NaBEt ₃ H (1 M, 9 μL) were added into a reaction vial with a volume of 8 mL. After 12 h of reaction, Quenched on exposure to air. Then the solvent was removed by rotary evaporation, and column chromatography (silica gel with a height of about 15 cm, a mixture of petroleum ether and ethyl acetate as eluent) gave a white solid.

The starting materials are all present when the catalyst precursors are 1a, 1b, 1c and 1d.

(R)-2-(2-Phenyl-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolyl-2-yl)ethyl)- 2,3-Dihydro-1hydro-naphthalene[1,8-de][1,3,2]oxadiazole boron: white solid (19.7 mg, 33%, 81ee%), purity > 97% by 1H spectrum. ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.26 (d, J = 4.3 Hz, 4H), 7.16(dt, J = 8.4, 4.3 Hz, 1H), 7.12 – 7.04 (m, 2H), 6.99 (d, J = 8.1 Hz, 2H),6.27 (d, J = 7.3 Hz, 2H), 5.81 (s, 2H), 2.92 (qd, J = 14.1, 8.1 Hz, 2H), 1.27(d, J = 11.4 Hz, 1H), 1.18 (s, 6H), 1.16 (s, 6H). ¹³ C NMR (101 MHz, CDCl ₃ ) δ143.7, 141.2, 136.2, 128.3, 128.2, 127.5, 125.7, 119.5, 117.3, 105.5, 83.3 ,31.9, 24.9, 24.5. ee values were measured by HPLC (OD-H column, i-PrOH:hexane = 5:95, 1.0 mL/min); (R)-isomer tr = 9.1 min, (S)-isomer tr = 10.8 min.[α] _D ²⁰ -11.2 (c 0.97, CH ₂ Cl2).

In summary, the experimental results show that the chiral pyridine bis-imidazole ligand-iron and cobalt complex of the present invention is used as a catalyst precursor, and pinacol borane is used as a boron reagent to make styryl-2,3- Asymmetric hydroboration of dihydro-1hydro-naphthalene[1,8-de][1,3,2]oxadiazole boron with low catalytic activity and moderate selectivity.

Finally, it is necessary to explain here that: the above-mentioned embodiments are only used to further describe the technical solutions of the present invention in detail, and cannot be interpreted as limiting the protection scope of the present invention. Non-essential improvements and adjustments all belong to the protection scope of the present invention.

Claims (9)

1. a chiral pyridine bis-imidazole ligand transition metal complex catalyst is characterized in that the structural formula of the catalyst is: General structural formula: Among them: M is a transition metal; R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ are hydrogen atoms, C1-C30 alkane groups or C6-C30 aryl groups ; X is a halogen atom or a halide metal salt ion; * means racemization or chirality, and when it is "chiral", it means R configuration or S configuration. 2. The chiral pyridine bis-imidazole ligand transition metal complex catalyst according to claim 1, characterized in that said M is iron or cobalt. 3. chiral pyridine bis-imidazole coordination transition metal complex catalyst according to claim 1, is characterized in that described X is: chlorine atom, bromine atom, iodine atom, cobalt tetrachloride ion, cobalt tetrabromide ions, cobalt tetraiodide ions, ferric tetrachloride ions, ferric tetrabromide ions or ferric tetraiodide ions. 4. The chiral pyridine bis-imidazole transition metal complex catalyst according to claim 1, characterized in that said R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ^8. R ⁹ is each independently hydrogen, C1-C6 alkyl or C6-C12 aryl. 5. The chiral pyridine bis-imidazole complex transition metal catalyst according to claim 4, characterized in that the C1-C6 alkyl group is: methyl, ethyl, propyl, isopropyl, butyl base, isobutyl or tert-butyl. 6. The chiral pyridine bis-imidazole coordination transition metal complex catalyst according to claim 4, characterized in that the aryl group of C6～C12 is: phenyl, 2,4,6-trimethylphenyl or 2,6-diisopropylphenyl. 7. A method for preparing the chiral pyridine bis-imidazole coordination transition metal complex catalyst according to any one of claims 1 to 6, characterized in that the specific steps of the method are: under an inert atmosphere, at 20 At ~30 °C, add the tetrahydrofuran solution of the chiral pyridine bis-imidazole ligand dropwise into the tetrahydrofuran solution of MX ₂ ; stir and react for 12 h; Metal complex catalyst; the molar ratio of the chiral pyridine bis-imidazole ligand to MX ₂ is 1:1-1:2. 8. The method according to claim 7, characterized in that the molar concentration of the THF solution of MX ₂ is 0.01 mol/liter to 0.1 mol/liter. 9. The method according to claim 7, characterized in that the molar concentration of the tetrahydrofuran solution of the chiral pyridine bis-imidazole ligand is 0.1 mol/liter to 1 mol/liter.