Chiral 2-oxazoline-8-imine-containing quinoline compounds and metal complexes thereof, and methods of making and using

Abstract

The application discloses a chiral 2-oxazoline-8-imine quinoline compound, the compound is high in optical purity, and a structural formula is shown in the following formula (1), and a preparation method thereof is disclosed. The application also discloses a metal complex obtained by complexing the chiral 2-oxazoline-8-imine quinoline compound with a transition metal salt, as shown in formula (6). The metal complex catalyst of the application can be used for preparing chiral or achiral alcohol compounds through catalytic hydrogenation of ketones of organic compounds, or the catalyst can be used for preparing chiral or achiral alkylsilane compounds through catalytic hydrosilylation of disubstituted olefins, and can be used for preparing chiral products with high regioselectivity and optical selectivity.

Description

Technical Field

[0001] This invention relates to a chemical method, specifically, to a metal complex containing a 2-oxazoline-8-iminequinoline compound and the use of the metal complex as a catalyst. Background Technology

[0002] Transition metal complex-catalyzed asymmetric reactions have attracted widespread attention from academia and industry worldwide, with extensive research on ligands linked to the central metal. Bisoxazoline ligands are a classic example, capable of forming complexes with many metals to catalyze numerous types of reactions [(a) H. Nishiyama, H. Sakaguchi, T. Nakamura, M. Horihata, M. Kondo, K. Itoh, Organometallics 1989, 8, 846. (b) D. Rechavi, M. Lemaire. Chem. Rev., 2002, 1023, 467. (c) G. Desimoni, G. Faita, P. Quadrelli. Chem. Rev., 2003, 103, 3119–3154]. [H. Liu, D.-M. Du, Adv. Synth. Catal. 2009, 351, 489.]. In 1956, Busch and Stoufer et al. first reported pyridine diimine, and its structure was subsequently confirmed [(a) RCStoufer, DH Busch J. Am. Chem. Soc. 1956, 78, 6016. (b) F. Lions, KV Martin J. Am. Chem. Soc. 1957, 79, 2733. (c) PE Figgins, DH Busch J. Am. Chem. Soc. 1959, 82, 820.]. It mainly coordinates with inexpensive metals (Fe, Co, Ni) to form catalysts and is widely used in the polymerization of olefins. Complexes of other transition metals have also been synthesized and used to catalyze organic reactions.

[0003] Amines play an indispensable role in nitrogen-containing drugs [Funayama, S. & Cordell, GA (eds) Alkaloids: A Treasury of Poisons and Medicines (Waltham, MA, 2014).], and the asymmetric reduction of imines is an efficient method for synthesizing chiral amine compounds. However, the reduction of imines involves optical selectivity issues. Therefore, developing efficient and highly optically selective imine hydrogenation reactions catalyzed by inexpensive metals is of great significance. Chiral secondary alcohols are widely present in drug molecules [R. Noyori, T. Ohkuma, Angew. Chem., Int. Ed., 2001, 40, 40–73.], and the asymmetric reduction of ketones is an important method for obtaining chiral secondary alcohols. However, the asymmetric reduction of ketones involves complex optical selectivity issues [(a)T.Ikariya,K.Murata,R.Noyori,Org.Biomol.Chem.,2006,4,393–406;(b)W.-C.Zhang,Y.-X.Chi,X.-M.Zhang,Acc.Chem.Res.,2007,40,1278–1290]. Therefore, developing efficient and highly optically selective ketone reduction reactions catalyzed by inexpensive metals is of great significance.

[0004] Organosilicon compounds are widely used in pharmaceuticals, materials, and other fields, and hydrosilylation is an effective method for constructing organosilicon compounds. Currently, the asymmetric hydrosilylation of internal alkenes still faces system limitations; only palladium-catalyzed systems can achieve highly efficient asymmetric transformations of olefin hydrosilylation [K. Kitayama, Y. Uozumi, T. Hayashi, J. Chem. Soc. Chem. Commun. 1995, 1533;]. Therefore, developing suitable catalytic systems to enrich the hydrosilylation of internal alkenes remains of significant research importance. Summary of the Invention

[0005] This invention discloses a 2-oxazoline-8-iminequinoline compound and its preparation method, wherein the SP2 carbon atom of the oxazoline ring is attached to the 2-position of the quinoline ring, and the 8-position of the quinoline ring is attached to the imine group. This invention also discloses a metal complex containing the 2-oxazoline-8-iminequinoline compound; and relates to the catalytic effect of this metal complex as a catalyst in optically selective chemical reactions, and in the asymmetric reductive transformation of disubstituted olefins into chiral alkylsilane compounds.

[0006] This invention is achieved through the following technical solution:

[0007] A chiral compound containing 2-oxazoline-8-iminequinoline, wherein the compound is of high optical purity and has the following structural formula (1):

[0008]

[0009] Where R 1 It is an unsubstituted C1-C12 alkyl group or a C5-C12 cyclo ...

[0010] R 2 It is H, an unsubstituted or C1-C12 alkyl group substituted with 1-2 C1-C4 alkoxy groups, an unsubstituted or C5-C12 cycloalkyl group substituted with 1-3 substituents A, or an unsubstituted or aryl B group substituted with 1-3 substituents B; wherein the aryl B group is phenyl or naphthyl; wherein the substituent A group is C1-C4 alkyl or C1-C4 alkoxy group; wherein the substituent B group is C1-C4 alkyl, C1-C4 alkoxy, C1-C4 fluoroalkyl, C1-C4 fluoroalkoxy, F, or Cl;

[0011] R 3 R 4 R 5 R 6 R 7 Each of the following is independently H, C1-C12 alkyl, C1-C4 fluoroalkoxy, F, Cl, nitro, or an unsubstituted or substituted C5-C12 cycloalkyl group, wherein the substituent A is a C1-C4 alkyl or C1-C4 alkoxy group;

[0012] R 8 R 9 Each of the following is independently H, an unsubstituted or C1-C12 alkyl group substituted with 1-2 C1-C4 alkoxy groups, an unsubstituted or C5-C12 cycloalkyl group substituted with 1-3 substituents A, or an unsubstituted or aryl A group substituted with 1-3 substituents B; wherein the aryl A group is benzyl, phenyl, or naphthyl; wherein the substituent A group is a C1-C4 alkyl or C1-C4 alkoxy group; wherein the substituent B group is a C1-C4 alkyl, C1-C4 alkoxy, C1-C4 fluoroalkyl, C1-C4 fluoroalkoxy, F, or Cl;

[0013] R 10It is an unsubstituted or substituted C1-C12 alkyl group, an unsubstituted or substituted C5-C12 cycloalkyl group, or an unsubstituted or substituted aryl group A, or an unsubstituted or substituted aryl group B; wherein the aryl group A is benzyl, phenyl, or naphthyl; wherein the substituent A is a C1-C4 alkyl or C1-C4 alkoxy group; wherein the substituent B is a C1-C4 alkyl, C1-C4 alkoxy, C1-C4 fluoroalkyl, C1-C4 fluoroalkoxy, F, or Cl;

[0014] In equation (1), * represents a chiral carbon atom.

[0015] The chiral compound containing 2-oxazoline-8-iminequinoline provided by the present invention is of high optical purity, wherein high optical purity means having enantioselectivity of 90% or more, preferably 95% or more, and more preferably 99% or more.

[0016] As a further improvement, the R described in this invention 1 Preferably, it is an unsubstituted cyclopentyl or cyclohexyl group or a group substituted with 1-3 substituents A, or an unsubstituted aryl group A or a group substituted with 1-4 substituents B; more preferably, it is an unsubstituted phenyl group or a group substituted with 1-3 substituents B, even more preferably, it is a phenyl group substituted with 1-2 C1-C4 alkyl groups, and even more preferably, it is 2,6-dimethylphenyl or 2,6-diisopropylphenyl.

[0017] R 2 Preferably, it is an unsubstituted C1-C12 alkyl group or a C1-C4 alkoxy group substituted with 1-2 C1-C4 alkoxy groups, or an unsubstituted aryl B group or a aryl B group substituted with 1-3 substituents B; more preferably, it is a C1-C12 alkyl group, and even more preferably, it is methyl, ethyl, isopropyl or tert-butyl.

[0018] Preferred R 3 R 4 R 5 R 6 R 7 Each is independently H or C1-C12 alkyl, more preferably H, methyl, ethyl, isopropyl or tert-butyl;

[0019] Preferred R 8 R 9 Each of the following is independently H, an unsubstituted or C1-C12 alkyl group substituted with 1-2 C1-C4 alkoxy groups, more preferably R. 8 R 9 It can be H, methyl, ethyl, isopropyl, or tert-butyl.

[0020] Preferred R 10 It is an unsubstituted or C1-C12 alkyl group substituted with 1-2 C1-C4 alkoxy groups, or an unsubstituted or aryl group A substituted with 1-3 substituents B; more preferably, it is R.10 It is a C1-C12 alkyl, phenyl, or benzyl, more preferably isopropyl, sec-butyl, ethyl, or benzyl.

[0021] The present invention also discloses a method for preparing a chiral compound containing 2-oxazoline-8-iminequinoline as shown in formula (1), the method comprising the following steps:

[0022] (a) The 2-bromo-8-acylquinoline compound shown in formula (2) and the amine compound shown in formula (3) undergo a condensation reaction under the action of a catalyst to obtain the compound shown in formula (4);

[0023] (b) Under nitrogen protection, the compound shown in formula (4) and the oxazoline compound shown in formula (5) undergo a coupling reaction catalyzed by transition metal inorganic salts, organophosphine ligands, and inorganic bases to prepare the chiral 2-oxazoline-8-iminequinoline compound shown in formula (1).

[0024]

[0025] R 1 ~R 10 The definition is as described above.

[0026] In step (a), the molar ratio of the 2-bromo-8-acylquinoline compound represented by formula (2) to the amine compound represented by formula (3) is 1:1-10, preferably 1:1-5, and more preferably 1:1-2.

[0027] Step (a) is carried out in the presence of a catalyst, which is a protic acid or molecular sieve, preferably p-toluenesulfonic acid, and the amount of the catalyst used is 1 to 5% of the amount of the 2-bromo-8-acylquinoline compound shown in formula (2).

[0028] The reaction solvent in step (a) is an organic solvent, preferably toluene, benzene, or xylene, and more preferably toluene. The volume of the reaction solvent in step (a) is 2 to 10 mL / mmol, calculated based on the amount of the 2-bromo-8-acylquinoline compound represented by formula (2).

[0029] The reaction in step (a) requires heating to reflux, water separation by a water separator, and reaction time of 10 to 30 hours.

[0030] After the reaction in step (a) is completed, the reaction solution is post-treated to obtain the compound shown in formula (4). The post-treatment method is as follows: after the reaction solution is cooled to room temperature, petroleum ether is added for dilution, followed by filtration and concentration, and column chromatography separation to obtain the compound shown in formula (4).

[0031] Step (b) is a coupling reaction catalyzed by transition metal Ru, Rh, Pd, Ir inorganic salts and organophosphine ligands, and inorganic bases.

[0032] Step (b) is carried out under the catalysis of a transition metal inorganic salt, an organophosphine ligand, and an inorganic base. The transition metal inorganic salt refers to the inorganic salts of Ru, Rh, Pd, and Ir, preferably palladium acetate. The inorganic base is preferably lithium tert-butoxide; the organophosphine ligand is preferably 1,2-bis(diphenylphosphine)ethane.

[0033] Step (b) is carried out in an organic solvent, which is any one of benzene, carbon tetrachloride, petroleum ether, tetrahydrofuran, dimethylformamide, diethyl ether, dichloromethane, chloroform, toluene, xylene, cyclohexane, n-hexane, n-heptane, dioxane, and acetonitrile, preferably dioxane. The volume of the reaction solvent used in step (b), calculated as the molar amount of the compound represented by formula (4), is 2 to 10 mL / mmol.

[0034] As a further improvement, the reaction temperature of the present invention is -0°C to 150°C, preferably heated to reflux for the reaction, and the reaction time is 1 hour to 48 hours.

[0035] As a further improvement, in step (b) of the present invention, the molar ratio of the compound represented by formula (4), the oxazoline compound represented by formula (5), the transition metal inorganic salt, the organophosphorus ligand, and the inorganic base is 1:1-5:0.01-1:0.02-2:2-10, preferably 1:1 to 3:0.01-0.1:0.02-0.1:2-4.

[0036] Step (b) is carried out under nitrogen protection. This reaction requires strict anhydrous and oxygen-free conditions. Therefore, before the reaction, it is preferable to freeze the reaction liquid with liquid nitrogen, evacuate it to a vacuum, melt it, and repeat this process three times to completely remove the air. After replenishing the nitrogen, the reaction is carried out under nitrogen protection. This is a commonly used method for anhydrous and oxygen-free treatment in this field.

[0037] In step (b), after the reaction is completed, the reaction solution is post-treated to obtain the chiral 2-oxazoline-8-iminequinoline compound represented by formula (1). The post-treatment method is as follows: the reaction solution is cooled to room temperature, filtered, washed with dichloromethane, concentrated, and then separated by column chromatography to obtain the chiral 2-oxazoline-8-iminequinoline compound represented by formula (1). The eluent used for column chromatography is a mixed solvent of petroleum ether and ethyl acetate.

[0038] This invention also discloses a chiral metal complex containing a 2-oxazoline-8-iminequinoline compound, wherein the metal complex is a salt ME of a transition metal of a chiral 2-oxazoline-8-iminequinoline compound and a transition metal of a transition metal of a periodic table element. nThe general formula of the chiral metal complex containing 2-oxazoline-8-iminequinoline compounds formed by the complexation reaction is shown in formula (6) below:

[0039]

[0040] In equation (6), R 1 -R 10 *As mentioned above;

[0041] In formula (6), M is a transition metal such as Fe, Co, Ni, Cu, Ag, Au, Ru, Rh, Pd, Os, or Ir;

[0042] E is any one of the following: halides (F, Cl, Br, I), pseudohalides (cyanides, cyanate, tetrafluoroborate, isocyanate), and anions of carboxylic acids, sulfonic acids, and phosphonic acids (carbonate, formate, acetate, propionate, methanesulfonate, trichloromethylsulfonate, phenylsulfonate, toluenesulfonate, phosphate, hexafluorophosphate).

[0043] n is the number of E, which can be 1, 2, or 3.

[0044] The chiral metal complex containing 2-oxazoline-8-iminequinoline compounds was prepared by the following method:

[0045] Under nitrogen protection, the chiral compound containing 2-oxazoline-8-iminequinoline and transition metal salt ME, as shown in formula (1), n The chiral metal complex containing a 2-oxazoline-8-iminequinoline compound, as shown in formula (6), is prepared by reacting in an organic solvent for 1 to 20 hours; the organic solvent is tetrahydrofuran or 2-methyltetrahydrofuran.

[0046] The chiral compound containing 2-oxazoline-8-iminequinoline and transition metal salt ME represented by formula (1) n The molar ratio of the substances is 0.9 to 2.2:1, preferably 0.9 to 1.1:1, and more preferably 1 to 1.1:1.

[0047] The synthesis of chiral metal complexes containing 2-oxazoline-8-iminequinoline compounds can be carried out at low or high temperatures, such as -20 to 150°C, but room temperature is preferred.

[0048] The present invention also provides the use of the chiral metal complex containing 2-oxazoline-8-iminequinoline compounds as shown in formula (6) as a catalyst.

[0049] The preferred amount of the metal complex used is 0.001-10 mol%, more preferably 0.1-5 mol%.

[0050] More specifically, the application is to carry out hydrosilylation or hydroboration reactions on carbon-carbon or carbon heteroatom double bonds of organic compounds in the presence of a catalyst, wherein the reaction is carried out in the presence of at least one metal complex of formula (6) in a catalytic amount.

[0051] Furthermore, the chiral metal complex containing 2-oxazoline-8-iminequinoline compounds can be used to catalyze the hydroboration of ketone compounds to produce alcohols. The ketone compounds can be alkyl ketones or aryl ketones, correspondingly generating alkyl alcohols or aryl alcohols. Moreover, the hydroboration reaction can yield chiral or achiral products. The enantioselectivity of the chiral products catalyzed by the metal complex of this application is very high, possessing significant application value. Preferably, the chiral metal complex containing 2-oxazoline-8-iminequinoline compounds is used to catalyze the hydroboration of aryl ketone compounds to produce chiral aryl alcohols.

[0052] The chiral metal complex containing a 2-oxazoline-8-iminequinoline compound can be used to catalyze the hydrosilylation of disubstituted olefin compounds to generate alkylsilane compounds. The disubstituted olefin compounds can be 1,1-disubstituted olefins (e.g., methyl lactones) or 1,2-disubstituted olefins, respectively, yielding alkylsilane compounds. The hydrosilylation reaction can yield chiral or achiral products. The enantioselectivity of the chiral products catalyzed by the metal complex of this application is very high, making it of significant application value. Preferably, the chiral metal complex containing a 2-oxazoline-8-iminequinoline compound is used to catalyze the hydrosilylation of α-methylstyrene or norbornene with diphenylsilane to generate chiral alkylsilane compounds.

[0053] Furthermore, the chiral metal complex containing 2-oxazoline-8-iminequinoline compounds can be used to catalyze the hydroboration of aryl ketones of formula (i) or the hydrosilylation of disubstituted alkenes of formulas (ii) and (iii).

[0054]

[0055] Specifically, the hydroboration reaction of formula (i) is carried out as follows: Under nitrogen protection, the chiral metal complex containing a 2-oxazoline-8-iminequinoline compound as shown in formula (6), along with pinacolborane and triethylborohydride, is dissolved in an organic solvent. Then, the aryl ketone compound as shown in formula (A) is added, and the reaction is stirred at room temperature for 1–24 h. The reaction solution is then post-treated to obtain the chiral aryl alcohol compound as shown in formula (B). The molar ratio of the aryl ketone compound as shown in formula (A), pinacolborane, triethylborohydride, and the chiral compound containing a 2-oxazoline-8-iminequinoline compound as shown in formula (6) is 1:1–1.5:0.01–0.1:0.01–0.1. The organic solvent can be diethyl ether. The post-treatment method of the reaction solution is generally as follows: quench the reaction with a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 3:1, concentrate the reaction solution, dilute the concentrate with a mixed solvent of petroleum ether and ethyl acetate, filter with silica gel, and separate by thin-layer chromatography to obtain the chiral aryl alcohol compound shown in formula (B). The developing solvent of the thin-layer chromatography is a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 5:1.

[0056] The hydrosilylation reactions of formulas (ii) and (iii) are preferably carried out as follows: Under nitrogen protection, the disubstituted olefin, diphenylsilane, and the chiral metal complex containing a 2-oxazoline-8-iminoquinoline compound of formula (6) are mixed evenly in an organic solvent, followed by the dropwise addition of sodium triethylborohydride and stirring at room temperature for 1–20 h. The resulting reaction solution is then post-treated to obtain the corresponding alkylsilane compound of formula (D) or (E). The molar ratio of the disubstituted olefin, diphenylsilane, sodium triethylborohydride, and the chiral metal complex containing a 2-oxazoline-8-iminoquinoline compound of formula (6) is 1:1–2:0.1–0.5:0.03–0.1. The organic solvent can be diethyl ether, toluene, or tetrahydrofuran. The post-treatment method of the reaction solution is generally as follows: quench the reaction with a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 20:1, concentrate the reaction solution, dilute the concentrate with a mixed solvent of petroleum ether and ethyl acetate, filter with silica gel, and separate by thin-layer chromatography to obtain the corresponding alkylsilane compound represented by formula (D) or formula (E), wherein the developing solvent of the thin-layer chromatography is petroleum ether.

[0057] In the chemical formula (i), the reactant formula (A) is an aryl ketone compound, and the R on the phenyl group... a The substituents on the benzene ring can be all H or 1 to 5 C substituents. The C substituents can be various groups, including but not limited to alkyl, cycloalkyl, aryl, heterocyclic aryl, hydroxyl, F, Cl, Br, I, nitro, amino, alkoxy, aldehyde, carboxyl, ester, mercapto, sulfonic acid, silyl, siloxy, etc.

[0058] In the chemical formulas (ii) and (iii), in the disubstituted olefins represented by formula (C) or (D), R b R c R d R e Each group can be alkyl, cycloalkyl, aryl, heterocyclic aryl, hydroxyl, F, Cl, Br, I, nitro, amino, alkoxy, aldehyde, carboxyl, ester, mercapto, sulfonic acid, silyl, siloxy, etc.; preferably alkyl groups of C1 to C20 and aryl groups of C6 to C12.

[0059] Or R d R e They can be linked together to form monocyclic or polycyclic cycloalkyl groups.

[0060] In the more preferred formula (C), R b For methyl, R c It is phenyl;

[0061] The preferred formula (D) is norbornene.

[0062] The beneficial effects of this invention are as follows:

[0063] This invention provides a novel chiral compound containing 2-oxazoline-8-iminequinoline.

[0064] This invention also provides a highly efficient synthesis route, with a total yield of up to 40% in two steps.

[0065] This invention provides a novel chiral compound containing 2-oxazoline-8-iminequinoline that can form stable metal complexes with transition metals Fe, Co, Ni, Cu, Ag, Au, Ru, Rh, Pd, Os, and Ir.

[0066] This invention also provides the use of the chiral metal complex containing 2-oxazoline-8-iminequinoline compounds as a homogeneous catalyst. The catalyst can be used to prepare chiral or achiral alcohols through the catalytic hydrogenation of ketones in organic compounds, or to prepare chiral or achiral alkylsilane compounds through the hydrosilylation of disubstituted alkenes. It is particularly useful for preparing chiral products with high regioselectivity and optical selectivity, with enantioselectivity reaching over 85%. The hydrosilylation of disubstituted alkenes is a reaction that is difficult to catalyze with existing catalysts. The metal complex catalyst of this invention solves this problem and achieves unexpected technical effects.

[0067] The preferred compound for reducing ketones is an open-chain or cyclic organic compound containing C=C and / or C=O groups, wherein the C=O group can be part of a cyclic system or an exocyclic group. The unsaturated compound can be an open-chain or cyclic ketone, α,β-diketone, α- or β-ketocarboxylic acid, or its α,β-ketoacetal or ketal.

[0068] The disubstituted olefin used for hydrosilylation of olefins can be an open-chain or cyclic olefin, including simple alkyl olefins and styrene derivatives. The olefin can be linked to other functional groups, such as ester carbonyl, ketone carbonyl, and other groups.

[0069] The chiral or achiral organic compounds prepared by the metal complex catalyst of this invention are active substances or intermediates for the preparation of such substances, and are particularly useful in the production of fragrances and flavorings, pharmaceutical preparations, and agrochemicals. Detailed Implementation

[0070] The technical solution of the present invention will be further described in detail below through specific embodiments:

[0071] The following examples illustrate the present invention. All reactions were carried out in airless nitrogen and degassed solvents. However, this does not limit the scope of the invention.

[0072] In the examples, the amine compounds represented by formula (3) are commercially available, and the 2-bromo-8-acylquinoline compounds represented by formula (2) are in accordance with literature (K). E. Pump, AEPazio, K. L. Cavallo, C. SlugovcBeilstein J. Org. Chem. 2015, 11, 1458.) were prepared. The oxazoline compounds shown in formula (5) were prepared according to the literature (J. Chen, T. Xi, Z. LuOrg. Chem. Front. 2018, 5, 247.).

[0073] Preparation of 2-bromo-8-acetylquinoline

[0074]

[0075] 2,8-Dibromoquinoline (19.62 g, 68.4 mmol, 1 equivalent) was added to a preheated, nitrogen-protected 250 mL three-necked flask, followed by diethyl ether (1 M, 70 mL). The flask was then placed at -78 °C, and butyllithium (34.2 mL, 82.1 mmol, 2.4 M) was slowly added dropwise. After the addition was complete, the mixture was stirred at this temperature for 1.5 hours. Then, N-acetyl-N,O-dimethylhydroxylamine (17.00 g, 164.2 mmol, 2.4 equivalents) was added dropwise to the reaction mixture at the same temperature. After the addition was complete, the mixture was slowly heated to room temperature. After the reaction of the starting materials was monitored by TLC and confirmed to be complete, a saturated ammonium chloride solution was added dropwise at 0°C. After separation, the mixture was extracted with ethyl acetate, dried with Na2SO4, concentrated, and separated by column chromatography to obtain the corresponding 2-bromo-8-acetylquinoline (9.38 g, 37.5 mmol, 55% yield).

[0076] Melting point: 92-94℃;

[0077] Infrared spectrum: IR (neat): 2962, 1681, 1562, 1457, 1263, 1101, 835, 766 cm⁻¹ -1 ;

[0078] 1H NMR spectrum: 1 H NMR: (400MHz, CDCl3): δ8.09-8.00(m,2H),7.99-7.91(m,1H),7.68-7.55(m,2H),2.97(s,3H);

[0079] Carbon NMR spectroscopy: 13 C NMR: (100MHz, CDCl3): δ202.3,145.7,141.9,138.5,138.2,131.5,131.1,127.0,126.7,126.2,32.7;

[0080] High-resolution mass spectrometry: HRMS (ESI-TOF) m / z: [M+H + ]CalcdforC 11 H8BrNO + 249.9862; Found 249.9864.

[0081] Synthetic method of 2-bromo-8-iminequinoline

[0082]

[0083] Taking A-2 as an example: 2-bromo-8-acetylquinoline (0.5007 g, 2.0 mmol), toluene (5 mL, 0.4 M), 2,6-diisopropylaniline (0.45 mL, 2.4 mmol, 1.2 equivalents), and p-toluenesulfonic acid monohydrate (0.0075 g, 0.04 mmol, 2 mol%) were added to a 100 mL round-bottom flask. The mixture was then refluxed after adding a water separator. The reaction was heated overnight. After the reaction solution cooled to room temperature, it was diluted with petroleum ether, filtered, concentrated, and separated by column chromatography to obtain a yellow viscous substance (0.4180 g, 1.02 mmol, 51% yield).

[0084] Example A1: (E)-1-(2-bromoquinolin-8-yl)-N-(2,6-dimethylphenyl)ethane-1-imine

[0085]

[0086] (E)-1-(2-bromoquinoline-8-yl)-N-(2,6-dimethylphenyl)ethane-1-imine (A-1) was prepared according to the above-described synthetic method for 2-bromo-8-imine quinoline. The following were used: 2-bromo-8-acetylquinoline (0.5007 g, 2 mmol), 2,6-dimethylimine (0.31 mL, 2.4 mmol, 1.2 equivalents), toluene (5 mL), and p-toluenesulfonic acid monohydrate (0.0075 g, 0.04 mmol). In the post-reaction treatment, column chromatography was performed using petroleum ether and ethyl acetate in a 10:1 volume ratio to give a yellow oily liquid (0.2950 g, 0.82 mmol, 41% yield).

[0087] Infrared spectrum: IR (neat): 1659, 1595, 1101, 842, 758 cm⁻¹ -1 ;

[0088] 1H NMR spectrum: 1 HNMR: (400MHz, CDCl3) δ7.97-7.85(m,2H),7.76(d,J=8.0Hz,1H),7.60-7.52(m,1H ),7.44(d,J=8.4Hz,1H),7.11-7.04(m,2H),6.97-6.90(m,1H),2.28-2.19(m,9H);

[0089] Carbon NMR spectroscopy: 13CNMR: (100MHz, CDCl3): δ170.0,148.3,145.9,141.2,140.6,138.1,128.8,128.5,127.7,126.8,126.7,125.8,125.7,122.8,22.4,17.9,17.8;

[0090] HRMS(ESI) calculated for [C 19 H 18 BrN2]+requiresm / z353.0648,foundm / z353.0663

[0091] Example A2: (E)-1-(2-bromoquinoline-8-yl)-N-(2,6-diisopropylphenyl)ethane-1-imine

[0092]

[0093] (E)-1-(2-bromoquinoline-8-yl)-N-(2,6-diisopropylphenyl)ethane-1-imine (A-2) was prepared according to the above-described synthetic method for 2-bromo-8-imine quinoline. The following were used: 2-bromo-8-acetylquinoline (0.5010 g, 2 mmol), 2,6-diisopropylimine (0.45 mL, 2.4 mmol, 1.2 equivalents), toluene (5 mL), and p-toluenesulfonic acid monohydrate (0.0075 g, 0.04 mmol). In the post-reaction treatment, column chromatography was performed using petroleum ether and ethyl acetate in a 10:1 volume ratio to give a yellow oily liquid (0.4180 g, 1.02 mmol, 51% yield).

[0094] Infrared spectrum: IR (neat): 2961, 1652, 1567, 1460, 1277, 1185, 1098, 836, 766 cm⁻¹ -1 ;

[0095] 1H NMR spectrum: 1 HNMR: (400MHz, CDCl3) δ8.03 (d, J = 8.4Hz, 1H), 7.90-7.35 (m, 2H), 7.68-7.62 (m, 1H), 7.55 (d ,J=8.4Hz,1H),3.29-3.16(m,2H),2.28(s,3H),1.33(d,J=6.8Hz,3H),1.21(d,J=6.8Hz,3H);

[0096] Carbon NMR spectroscopy: 13CNMR: (100MHz, CDCl3): δ170.4,146.1,145.7,141.4,141.3,138.2,136.8,128.4,128.4,127.1,126.1,123.7,123.0,27.9,23.5,23.2;

[0097] High-resolution mass spectrometry: HRMS (ESI-TOF) m / z: [M+H + ]CalcdforC 23 H 26 BrN2 + 409.1274; Found 409.1276.

[0098] B) Preparation of compound B containing 2-oxazoline-8-iminoquinoline

[0099]

[0100] Method for preparing chiral ligands of 2-oxazoline-8-iminequinoline (B)

[0101] Taking B-5 as an example: In a Shrek tube with a reflux condenser and nitrogen protection after baking, lithium tert-butoxide (0.3303 g, 4.0 mmol, 3.6 mol%) was added to a 6 mL solution of 1,4-dioxane containing imine A-2 (0.4579 g, 1.1 mmol), (S)-4-ethyl-4,5-dihydrooxazole (0.2032 g, 2.0 mmol, dissolved in DMF, DMF:oxazole volume ratio = 1:1), palladium acetate (0.0121 g, 0.05 mmol, 4.6 mol%), and 1,2-bis(diphenylphosphine)ethane (0.0233 g, 0.056 mmol, 5.1 mol%). The reaction mixture was then subjected to a freeze-evacuation-thaw cycle three times. After reflux for 41 hours, the mixture was cooled to room temperature and filtered through silica gel, using dichloromethane as a washing agent. After concentrating the solution, column chromatography was performed (petroleum ether and ethyl acetate volume ratio 5:1) to obtain a yellow oily substance (0.2428 g, 0.57 mmol, 57% yield).

[0102] Example B1: Preparation of compound B-1 containing 2-oxazoline-8-iminequinoline

[0103]

[0104] (S,E)-N-(2,6-dimethylphenyl)-1-(2-(4-ethyl-4,5-dihydrooxazol-2-yl)quinolin-8-yl)ethane-1-imine (B-1) was prepared according to the method for preparing 2-oxazoline-8-iminequinoline. A-1 (0.4579 g, 1.3 mmol), (S)-4-ethyl-4,5-dihydrooxazol (0.1983 g, 2.6 mmol), and palladium acetate were used. ( 0.0152 g, 0.065 mmol), 1,2-bis(diphenylphosphine)ethane (dppe) (0.0300 g, 0.073 mmol), lithium tert-butoxide (0.4265 g, 5.2 mmol) reacted with 1,4-dioxane (8 mL) and separated by column chromatography (PE / EA / Et3N volume ratio = 3 / 1 / 0.03) to give a yellow liquid (0.2622 g, 0.70 mmol, 54% yield);

[0105] Specific rotation: [α] 20 D = -87.8 (c0.79, CHCl3);

[0106] 1H NMR spectrum: 1 HNMR: (400MHz, CDCl3): δ8.21-8.08(m,2H),7.96-7.89(m,1H),7.8C-Co.76(m,1H),7.62-7.53(m,1H),7.06-6.96(m,2H),6.90-6.83 (m,1H),4.53-4.45(m,1H),4.32-4.20(m,1H),4.10-4.02(m,1H),2.27(s,3H),2.17(s,6H),1.80-1.53(m,2H),0.96(t,J=7.2Hz,3H);

[0107] Carbon NMR spectroscopy: 13 C NMR: (100MHz, CDCl3): δ171.0,163.6,148.6,146.5,145.3,142.2,136.4,128.5,128.5,1 28.4,127.8,127.7,126.2,126.2,122.8,121.0,72.6,68.3,28.6,22.9,18.0,18.0,10.1;

[0108] High-resolution mass spectrometry: HRMS (ESI-TOF) m / z: [M+H + ]Calcd for C 24 H 26 N3O+ 372.2070; Found 372.2072.

[0109] Example B2: Preparation of compound B-2 containing 2-oxazoline-8-iminequinoline

[0110]

[0111] (S,E)-1-(2-(4-benzyl-4,5-dihydrooxazol-2-yl)quinoline-8-yl)-N-(2,6-dimethylphenyl)ethane-1-imine (B-2) was prepared according to the standard method for the preparation of 2-oxazoline-8-iminequinoline. A-1 (0.4579 g, 1.3 mmol), (S)-4-benzyl-4,5-dihydrooxazol (0.4032 g, 2.5 mmol), and palladium acetate were used. ( 0.0156 g, 0.065 mmol), 1,2-bis(diphenylphosphine)ethane (dppe) (0.0301 g, 0.073 mmol), lithium tert-butoxide (0.4622 g, 5.2 mmol) reacted with 1,4-dioxane (8 mL) and separated by column chromatography (PE / EA / Et3N = 3 / 1 / 0.03) to give a yellow liquid (0.2394 g, 0.70 mmol, 42% yield);

[0112] Specific rotation: [α] 20 D = -59.8 (c1.02, CHCl3);

[0113] 1H NMR spectrum: 1 H NMR: (400MHz, CDCl3) δ8.28-8.19(m,2H),8.0C-Co.97(m,1H),7.93-7.87(m ,1H),7.71-7.63(m,1H),7.37-7.20(m,5H),7.11-7.05(m,2H),6.98-6.88( m,1H),4.74-4.63(m,1H),4.51-4.41(m,1H),4.28-4.20(m,1H),3.28(dd,J =5.6,13.6Hz,1H),2.81(dd,J=8.8,13.6Hz,1H),2.34(s,3H),2.24(s,6H);

[0114] Carbon NMR spectroscopy: 13C NMR: (100MHz, CDCl3) δ170.9,164.0,148.6,146.4,145.3,142.2,137.8,136.5,129.2,128.6, 128.6,128.5,128.5,127.8,126.6,126.2,126.2,122.8,121.0,72.4,68.2,41.7,22.9,18.0;

[0115] High-resolution mass spectrometry: HRMS (ESI-TOF) m / z: [M+H + ]CalcdforC 29 H 28 N3O + 434.2227; Found 434.2228.

[0116] Example B3: Preparation of compound B-3 containing 2-oxazoline-8-iminequinoline

[0117]

[0118] (S,E)-N-(2,6-dimethylphenyl)-1-(2-(4-isopropyl-4,5-dihydrooxazol-2-yl)quinoline-8-yl)ethane-1-imine (B-3) was prepared according to the standard method for the preparation of 2-oxazoline-8-iminequinoline. A-1 (0.4579 g, 1.3 mmol), (S)-4-isopropyl-4,5-dihydrooxazol (0.2263 g, 2.0 mmol), and palladium acetate were used. ( 0.0151 g, 0.065 mmol), 1,2-bis(diphenylphosphine)ethane (dppe) (0.0294 g, 0.073 mmol), lithium tert-butoxide (0.4231 g, 5.2 mmol) reacted with 1,4-dioxane (8 mL) and separated by column chromatography (PE / EA / Et3N = 3 / 1 / 0.03) to give a yellow liquid (0.3751 g, 0.70 mmol, 75% yield);

[0119] Specific rotation: [α] 20 D = -104.0 (c2.0, CHCl3);

[0120] Infrared spectrum: IR (neat): 2962, 1644, 1566, 1468, 1364, 1094, 850, 766 cm⁻¹ -1 ;

[0121] 1H NMR spectrum: 1H NMR: (400MHz, CDCl3) δ8.25-8.18(m,2H),8.01-7.96(m,1H),7.90-7.84(m,1H),7.68-7.60(m,1H),7.12-7.05(m,2H),6.98-6.91(m, 1H),4.57-4.46(m,1H),4.27-4.12(m,2H),2.35(s,3H),2.26(s,6H),1.96-1.85(m,1H),1.08(d,J=6.8Hz,3H),0.97(d,J=6.8Hz,3H);

[0122] Carbon NMR spectroscopy: 13 CNMR: (100MHz, CDCl3): δ171.0,163.6,148.6,146.5,145.3,142.2,136.4,128.5,128.5,1 28.4,127.8,127.7,126.2,126.2,122.8,121.0,72.6,68.3,28.6,22.9,18.0,18.0,10.1;

[0123] High-resolution mass spectrometry: HRMS (ESI-TOF) m / z: [M+H + ]Calcd for C 25 H 28 N3O + 386.2227; Found 386.2229.

[0124] Example B4: Preparation of compound B-4 containing 2-oxazoline-8-iminequinoline

[0125]

[0126] (E)-1-(2-((S)-4-((R)-sec-butyl)-4,5-dihydrooxazol-2-yl)quinoline-8-yl)-N-(2,6-dimethylphenyl)ethane-1-imine (B-4) was prepared according to the standard method for the preparation of 2-oxazoline-8-iminequinoline. A-1 (0.4579 g, 1.3 mmol), (S)-4-sec-butyl-4,5-dihydrooxazol (0.2544 g, 2.0 mmol), and palladium acetate were used. (0.0156 g, 0.065 mmol), 1,2-bis(diphenylphosphine)ethane (dppe) (0.0320 g, 0.073 mmol), lithium tert-butoxide (0.5262 g, 6.6 mmol) reacted with 1,4-dioxane (8 mL) and separated by column chromatography (PE / EA / Et3N = 3 / 1 / 0.03) to give a yellow liquid (0.1902 g, 0.48 mmol, 37% yield);

[0127] Specific Rotation: [α] 20 D = -89.2 (c1.05, CHCl3);

[0128] Infrared spectrum: IR (neat): 2964, 1644, 1567, 1467, 1364, 1094, 850, 767 cm⁻¹ -1 ;

[0129] 1H NMR spectrum: 1 HNMR: (400MHz, CDCl3) δ8.27-8.19(m,2H),8.02-7.91(m,1H),7.92-7.87( m,1H),7.70-7.63(7.12-7.06,m,1H),7.12-7.06(m,2H),6.98-6.91(m,1H) ,4.53-4.46(m,1H),4.36-4.27(m,1H),4.27-4.20(m,1H),2.34(s,3H),2. 25(s,6H),1.85-1.62(m,2H),0.99(t,J=7.6Hz,3H),0.91(d,J=6.8Hz,3H);

[0130] Carbon NMR spectroscopy: 13 CNMR: (100MHz, CDCl3) δ171.0,163.4,148.6,146.6,145.3,142.3,136.4,128.6,128.5,1 28.4,127.8,127.7,126.3,122.8,121.0,71.6,70.2,39.2,26.1,22.9,18.0,14.5,11.6;

[0131] High-resolution mass spectrometry: HRMS (ESI-TOF) m / z: [M+H + ]CalcdforC 26 H 30 N3O + 400.2383; Found 400.2382.

[0132] Example B5: Preparation of compound B-5 containing 2-oxazoline-8-iminequinoline

[0133]

[0134] (S,E)-N-(2,6-diisopropylphenyl)-1-(2-4-ethyl-4,5-dihydrooxazol-2-yl)quinoline-8-yl)ethane-1-imine (B-5) was prepared according to the standard method for the preparation of 2-oxazoline-8-iminequinoline. A-2 (0.4579 g, 1.1 mmol), (S)-4-ethyl-4,5-dihydrooxazol (0.2032 g, 2.0 mmol, DMF / oxazoline 1 / 1), and palladium acetate were used. ( 0.0121 g, 0.05 mmol), 1,2-bis(diphenylphosphine)ethane (dppe) (0.0233 g, 0.056 mmol), lithium tert-butoxide (0.3303 g, 4.0 mmol) reacted with 1,4-dioxane (6 mL) and separated by column chromatography (PE / EA / Et3N = 3 / 1 / 0.03) to give a yellow liquid (0.2428 g, 0.57 mmol, 57% yield);

[0135] Specific rotation: [α] 20 D = -78.2 (c1.03, CHCl3);

[0136] 1H NMR spectrum: 1 HNMR: (400MHz, CDCl3) δ8.29-8.18(m,2H),7.97-7.85(m,2H),7.72-7.63(m,1H),7.23-7.18(m,2H),7.16-7.08(m,1H),4.64-4.52(m,1H) ),4.42-4.28(m,1H),4.19-4.08(m,1H),2.39(s,3H),1.91-1.58(m,2H),1.31(d,J=7.2Hz,6H),1.23-1.15(m,6H),1.05(t,J=7.2Hz,3H);

[0137] Carbon NMR spectroscopy: 13CNMR: (100MHz, CDCl3) δ171.2,163.7,146.5,145.9,142.6,136.9,136.4,128.5,128.4,12 8.3,127.8,123.6,122.9,121.1,72.6,68.3,28.6,27.9,23.48,23.46,23.44,23.1,10.1;

[0138] High-resolution mass spectrometry: HRMS (ESI-TOF) m / z: [M+H + ]CalcdforC 28 H 34 N3O + 428.2696; Found 428.2696.

[0139] Example B6: Preparation of compound B-6 containing 2-oxazoline-8-iminequinoline

[0140]

[0141] (S,E)-1-(2-(4-benzyl-4,5-dihydrooxazol-2-yl)quinoline-8-yl)-N-(2,6-diisopropylphenyl)ethane-1-imine (B-6) was prepared according to the standard method for the preparation of 2-oxazoline-8-iminequinoline. A-2 (0.4089 g, 1.0 mmol), (S)-4-benzyl-4,5-dihydrooxazol (0.2418 g, 1.5 mmol), and palladium acetate were used. ( 0.0120 g, 0.05 mmol), 1,2-bis(diphenylphosphine)ethane (dppe) (0.0251 g, 0.056 mmol), lithium tert-butoxide (0.3642 g, 4.5 mmol) reacted with 1,4-dioxane (6 mL) and separated by column chromatography (PE / EA / Et3N = 3 / 1 / 0.03) to give a yellow liquid (0.2789 g, 0.57 mmol, 57% yield);

[0142] Specific rotation: [α] 20 D = -13.1 (c1.37, CHCl3);

[0143] Infrared spectrum: IR (neat): 2962, 1642, 1567, 1461, 1362, 1097, 850, 767 cm⁻¹ -1 ;

[0144] 1H NMR spectrum: 1H NMR: (400.0MHz, CDCl3) δ8.28-8.21(m,2H),7.98-7.86(m,2H),7.72-7.63(m,1H),7.37-7.07(m,8H),4.76-4.64(m,1H),4.51-4.41(m,1H),4.28 -4.18(m,1H),3.30(dd,J=5.2,13.6Hz,1H),3.27-3.17(m,1H),2.81(dd ,J=8.8,13.6Hz,1H),2.37(s,3H),1.33-1.26(m,6H),1.23-1.16(m,6H);

[0145] Carbon NMR spectroscopy: 13 C NMR: (100.6MHz, CDCl3) δ171.2,164.1,146.4,145.8,145.3,142.6,137.7,136.9,136.9,136.4,129.2,128. 6,128.4,128.3,127.9,126.6,123.6,122.9,122.9,121.0,72.4,68.1,41.7,27.93,27.92,23.5,23.4,23.1;

[0146] High-resolution mass spectrometry: HRMS (ESI-TOF) m / z: [M+H + ]Calcd for C 33 H 36 N3O + 490.2853; Found 490.2855.

[0147] Example B7: Preparation of compound B-7 containing 2-oxazoline-8-iminequinoline

[0148]

[0149] (S,E)-N-(2,6-diisopropylphenyl)-1-(2-(4-isopropyl-4,5-dihydrooxazol-2-yl)quinoline-8-yl)ethane-1-imine (B-7) was prepared according to the standard method for the preparation of 2-oxazoline-8-iminequinoline. A-2 (0.4071 g, 1.0 mmol), (S)-4-isopropyl-4,5-dihydrooxazol (0.1697 g, 1.5 mmol), and palladium acetate were used. (0.0141 g, 0.05 mmol), 1,2-bis(diphenylphosphine)ethane (dppe) (0.0280 g, 0.056 mmol), lithium tert-butoxide (0.3284 g, 4.0 mmol) reacted with 1,4-dioxane (6 mL) and separated by column chromatography (PE / EA / Et3N = 3 / 1 / 0.03) to give a yellow liquid (0.2456 g, 0.56 mmol, 56% yield);

[0150] Specific rotation: [α] 20 D = -60.5 (c1.54, CHCl3);

[0151] Infrared spectrum: IR (neat): 2962, 1644, 1566, 1463, 1362, 1095, 850, 767 cm⁻¹ -1 ;

[0152] 1H NMR spectrum: 1 H NMR: (400MHz, CDCl3) δ8.28-8.20(m,2H),7.97-7.92(m,1H),7.86-7.92(m,1H),7.71-7.64(m,1H),7.2C-Co.18(m,2H),7.16-7.09(m,1H),4.57-4 .46(m,1H),4.27-4.16(m,2H),3.30-3.17(m,2H),2.39(s,3H),1.36-1.2 7(m,6H),1.23-1.16(m,6H),1.08(d,J=6.8Hz,3H),0.98(d,J=6.8Hz,3H);

[0153] Carbon NMR spectroscopy: 13 C NMR: (100MHz, CDCl3) δ171.3,163.6,146.6,145.9,145.3,142.6,136.9,136.3,128.5,128.4,128.3, 127.8,123.6,122.9,122.9,121.1,72.9,70.7,32.9,28.0,27.9,23.5,23.4,23.2,23.2,19.0,18.2;

[0154] High-resolution mass spectrometry: HRMS (ESI-TOF) m / z: [M+H + ]CalcdforC 29 H 36 N3O + 442.2853; Found 442.2854.

[0155] Example B8: Preparation of compound B-8 containing 2-oxazoline-8-iminequinoline

[0156]

[0157] (E)-1-(2-((S)-4-(R)-sec-butyl)-4,5-dihydrooxazol-2-yl)quinoline-8-yl)-N-(2,6-diisopropylphenyl)ethane-1-imine (B-8) was prepared according to the standard method for the preparation of 2-oxazoline-8-iminequinoline. A-2 (0.4075 g, 1.0 mmol), (S)-4-((R)-sec-butyl)-4,5-dihydrooxazol (0.1697 g, 1.3 mmol), and palladium acetate were used. ( 0.0120 g, 0.05 mmol), 1,2-bis(diphenylphosphine)ethane (dppe) (0.0245 g, 0.056 mmol), lithium tert-butoxide (0.3284 g, 4.0 mmol) reacted with 1,4-dioxane (6 mL) and separated by column chromatography (PE / EA / Et3N = 3 / 1 / 0.03) to give a yellow liquid (0.3554 g, 0.78 mmol, 78% yield);

[0158] Infrared spectrum: IR (neat): 2961, 1642, 1568, 1460, 1363, 1094, 849, 766 cm⁻¹ -1 ;

[0159] Specific rotation: [α] 20 D = -82.6 (c2.58, CHCl3);

[0160] 1H NMR spectrum: 1 H NMR: (400.1MHz, CDCl3) δ8.27-8.20(m,2H),7.97-7.92(m,1H),7.92-7.87(m,1H) ,7.71-7.64(m,1H),7.23-7.16(m,2H),7.15-7.09(m,1H),4.52-4.45(m,1H),4.37 -4.27(m,1H),4.25-4.18(m,1H),3.29-3.16(m,2H),2.39(s,3H),1.83-1.61(m,2H ),1.36-1.22(m,7H),1.22-1.14(m,6H),1.02-0.96(m,3H),0.92(d,3H,J=6.8Hz);

[0161] High-resolution mass spectrometry: HRMS (ESI-TOF) m / z: [M+H + ]Calcd for C 30 H 38 N3O + 456.3009; Found 456.3010.

[0162] c) Preparation of metal complex C

[0163] 2-OIQ Cobalt Chloride (C-Co) Synthesis Method

[0164]

[0165] Taking C-Co1 as an example: Ligand B-1 (0.0965 g, 0.26 mmol, 1.05 equivalents), tetrahydrofuran (3 mL), and anhydrous cobalt chloride (0.0326 g, 0.25 mmol, 1 equivalent) were added sequentially to a 25 mL Shrek tube under nitrogen protection after baking. The reaction solution was stirred overnight for 12 hours, then diluted with 10 mL of diethyl ether, stirred for 10 minutes, filtered, washed twice with anhydrous diethyl ether, and the solid was dried under vacuum to obtain the corresponding complex (0.0960 g, 0.19 mmol, 77% yield).

[0166] Example C1:

[0167]

[0168] (C-Co1) was obtained by the above-described synthesis of 2-OIQ cobalt chloride (C-Co). The brown cobalt complex C-Co1 (0.0960 g, 0.19 mmol, 77% yield) was obtained by filtration and drying using B-1 (0.0965 g, 0.26 mmol, 1.05 equivalent), THF (3 mL), and anhydrous cobalt chloride CoCl2 (0.0326 g, 0.25 mmol).

[0169] Elemental analysis: Anal.CalcdforC 24 H 25 Cl2CoN3O+0.5H2O:C,56.49;H,5.14;N,8.23;Found:C,56.27;H,5.02;N,8.09.

[0170] Example C2:

[0171]

[0172] (C-Co2) was obtained using the standard method for preparing 2-OIQ cobalt chloride (C-Co). The cobalt complex C-Co2 (0.0910 g, 0.21 mmol, 1.05 equivalents), THF (2 mL), and anhydrous cobalt chloride CoCl2 (0.0258 g, 0.2 mmol) was filtered and dried to yield a brown cobalt complex C-Co2 (0.0908 g, 0.16 mmol, 81% yield).

[0173] Elemental analysis: Anal.CalcdforC 29 H 27 Cl2CoN3O+0.5H2O:C,60.85;H,4.93;N,7.34;Found:C,60.93;H,4.96;N,7.08

[0174] Example C3:

[0175]

[0176] (C-Co3) was obtained using the standard method for preparing 2-OIQ cobalt chloride (C-Co), and the brown cobalt complex C-Co3 (0.0811 g, 0.15 mmol, 77% yield) was obtained by filtration and drying using B-4 (0.0839 g, 0.21 mmol, 1.05 equivalent), THF (2 mL), and anhydrous cobalt chloride CoCl2 (0.0255 g, 0.2 mmol).

[0177] Elemental analysis: Anal.CalcdforC 26 H 29 Cl2CoN3O+0.5H2O:C,58.00;H,5.62;N,7.81;Found:C,58.67;H,5.53;N,7.71.

[0178] Example C4:

[0179]

[0180] (C-Co4) was obtained using the standard method for the preparation of 2-OIQ cobalt chloride (C-Co). The cobalt complex C-Co4 (0.1796 g, 0.42 mmol, 1.05 equivalents), THF (4 mL), and anhydrous cobalt chloride CoCl2 (0.0519 g, 0.4 mmol) was obtained by filtration and drying using B-5 (0.1796 g, 0.42 mmol, 80% yield). Elemental analysis: Anal. Calcd for C 28 H 33Cl2CoN3O+H2O:C,58.44;H,6.13;N,7.30;Found:C,58.59;H,6.05;N,7.26.

[0181] Example C5:

[0182]

[0183] (C-Co5) was obtained using the standard method for the preparation of 2-OIQ cobalt chloride (C-Co). The cobalt complex C-Co5 (0.1829 g, 0.36 mmol, 73% yield) was obtained by filtration and drying using B-6 (0.1831 g, 0.37 mmol, 1.05 equivalent), THF (4 mL), and anhydrous cobalt chloride CoCl2 (0.0461 g, 0.35 mmol). Elemental analysis: Anal. Calcd for C 33 H 35 Cl2CoN3O+0.5H2O: C, 63.06; H, 5.77; N, 6.69; Found: C, 63.40; H, 5.65; N, 6.65.

[0184] Example C6:

[0185]

[0186] (C-Co6) was obtained using the standard method for the preparation of 2-OIQ cobalt chloride (C-Co). The cobalt complex C-Co6 (0.1831 g, 0.32 mmol, 80% yield) was obtained by filtration and drying using B-7 (0.1853 g, 0.42 mmol, 1.05 equivalent), THF (4 mL), and anhydrous cobalt chloride CoCl2 (0.0513 g, 0.4 mmol). Elemental analysis: Anal. Calcd for C 29 H 35 Cl2CoN3O+H2O:C,59.09;H,6.33;N,7.13;Found:C,59.77;H,6.25;N,6.92.

[0187] d) Asymmetric hydroboration of arylalkyl ketones catalyzed by metal complex C-Co3

[0188]

[0189] In a 25 mL Shrek tube heated under nitrogen protection, the metal complex C-Co3 (0.0125 mmol, 2.5 mol%), diethyl ether (0.5 mL, 1.0 M), and pinacol borane (0.6 mmol, 1.2 equivalents) were added sequentially. After the addition was complete, sodium triethylborohydride (12.5 μL, 0.0125 mmol, 2.5 mol%) was added dropwise. The mixture was stirred at room temperature for one minute, and then acetophenone (0.0601 g, 0.5 mmol, 1 equivalent) was added dropwise. The mixture was stirred overnight at room temperature. The reaction was then quenched using a 3:1 volume ratio of petroleum ether and ethyl acetate. The reaction solution was then concentrated, and the concentrate was diluted with a 3:1 volume ratio of petroleum ether and ethyl acetate. The solution was filtered with silica gel assisted, concentrated, and then subjected to coarse spectral identification with an internal standard. The remaining solution was subjected to thin-layer chromatography on a thick preparative plate with a 5:1 ratio of petroleum ether / ethyl acetate as the developing solvent. After separation, the solution was dissolved in n-hexane, filtered through a filter, and the liquid phase sample was prepared.

[0190] Example D1: 1-phenylethan-1-ol phenylethanol

[0191]

[0192] Oily liquid, 77% yield, 61% ee. HPLC conditions: Chiralcel AS-H, n-hexane / i-PrOH = 98 / 2, 1.0 mL / min, n = 220 nm, t r 11.9 (major), 13.1 (minor); 1 ¹H NMR: (400.1 MHz, CDCl₃) δ 7.40–7.31 (m, 4H), 7.30–7.24 (m, 1H), 4.92–4.83 (m, 1H), 1.98 (d, J = 2.0 Hz, 1H), 1.48 (d, J = 6.4 Hz, 3H); product data consistent with known compounds [J. Guo, J. Chen, Z. Lu Chem. Commun. 2015, 51, 5725–5727.]

[0193] e) Asymmetric hydrosilylation of olefins catalyzed by C-Co metal complexes

[0194] In a 25 mL Shrek tube heated under nitrogen protection, catalyst (0.01 mmol, 5 mol%), tetrahydrofuran (1 mL, 0.2 M), olefin (0.2 mmol, 1 equivalent), and diphenylsilane (0.3 mmol, 1.5 equivalent) were added sequentially. After the addition was complete, sodium triethylborohydride (30 μL, 0.03 mmol, 15 mol%) was added dropwise, and the mixture was stirred at room temperature for approximately 12 hours. The reaction was then quenched using a 20:1 volume ratio of petroleum ether and ethyl acetate. The reaction solution was then concentrated, and the concentrate was diluted with a 20:1 volume ratio of petroleum ether and ethyl acetate, filtered with silica gel, concentrated again, and identified by a coarse chromatogram using an internal standard. The residue was separated by thin-layer chromatography using a thick preparative plate with petroleum ether as the developing solvent. After separation, the residue was dissolved in n-hexane, filtered through a filter tip, and a liquid phase sample was prepared.

[0195] Example E1: diphenyl(2-phenylpropyl)silane

[0196] Diphenyl(2-phenylpropyl)silane

[0197]

[0198] Using C-Co3 as a catalyst, the product was an oily liquid with a yield of 91%. HPLC conditions: Chiralcel AD-H, n-hexane / i-PrOH = 98 / 2, 1 mL / min, n = 220 nm, tr 20.5 (major), 22.3 (minor); 1 ¹H NMR: (400.1 MHz, CDCl₃) δ 7.60–7.46 (m, 4H), 7.42–7.29 (m, 6H), 7.28–7.20 (m, 2H), 7.20–7.10 (m, 3H), 4.77 (t, J = 3.6 Hz, 1H), 3.02–2.88 (m, 1H), 1.65–1.48 (m, 2H), 1.31 (d, 3H); Product data consistent with known compounds [Chen, J.; Cheng, B.; Cao, M.; Lu, Z. Angew. Chem. Int. Ed. 2015, 54, 4661.]

[0199] Comparative example:

[0200] The metal complex 8-OIQCoCl2, prepared from the chiral ligand of 2-imine-8-oxazoline and CoCl2, was used as a catalyst. The preparation method is described in CN113880822A. The substituent on the imine was 2,6-dimethylphenyl, and the substituent at position 4 on the dihydrooxazol was sec-butyl. The structural formula is shown in the reaction formula in Example E1. The results indicate that the reaction yield catalyzed by this catalyst is extremely low, and it is almost impossible to catalyze the reaction.

[0201] Example F: Comparative Experiment of Catalytic Performance and Reaction Conditions of Various Catalysts

[0202]

[0203]

[0204] a. Reaction conditions: olefin (0.2 mmol, 1 equivalent), diphenylsilane (0.3 mmol, 1.5 equivalent), 2-OIQ ferrous chloride or 2-OIQ cobalt chloride (0.01 mmol, 5 mol%) as catalyst, triethylborohydride (0.03 mmol, 15 mol%), tetrahydrofuran (1 mL, 0.2 M), reacted overnight at room temperature under a nitrogen atmosphere. All yields were NMR yields; ee values ​​were determined by liquid chromatography using an OJ-H column.

[0205] b uses toluene as a solvent; c uses diethyl ether as a solvent.

[0206]

[0207] Oily liquid, 91% yield (catalyst C-Co2). HPLC conditions: Chiralcel OJ-H, n-hexane / i-PrOH = 99 / 1, 0.5 mL / min, n = 220 nm, tr 9.7 (minor), 10.4 (major). 1 ¹H NMR: (400.1 MHz, CDCl₃) δ 7.65–7.49 (m, 4H), 7.45–7.28 (m, 6H), 4.69 (d, J = 5.4 Hz, 1H), 2.35–2.22 (m, 2H), 1.65–1.45 (m, 4H), 1.36–1.19 (m, 4H), 1.16–1.05 (m, 1H); Product data consistent with known compounds [Chen, J.; Cheng, B.; Cao, M.; Lu, Z. Angew. Chem. Int. Ed. 2015, 54, 4661.]

[0208] The above examples are only some specific embodiments of the present invention. Obviously, the present invention is not limited to the above embodiments and there can be many variations. All variations that can be directly derived or conceived by those skilled in the art from the content disclosed in the present invention should be considered to be within the protection scope of the present invention.

Claims

1. A chiral compound containing 2-oxazoline-8-iminequinoline, wherein the compound is of high optical purity and has the structural formula shown in formula (1) below, wherein high optical purity means having enantioselectivity of more than 90%: (1)； Where R 1 It is an unsubstituted or substituted phenyl group with 1-4 substituents B; wherein the substituents B are C1-C4 alkyl or C1-C4 alkoxy. R 2 It is an unsubstituted or C1-C12 alkyl group substituted with 1-2 C1-C4 alkoxy groups; R 3 R 4 R 5 R 6 R 7 Each is independently H or C1-C12 alkyl; R 8 R 9 Each is independently H, an unsubstituted C1-C12 alkyl group or a C1-C4 alkyl group substituted with 1-2 C1-C4 alkoxy groups; R 10 It is an unsubstituted or substituted C1-C12 alkyl group, an unsubstituted or substituted C5-C12 cycloalkyl group, or an unsubstituted or substituted aryl group A, or an unsubstituted or substituted aryl group B; wherein the aryl group A is benzyl, phenyl, or naphthyl; wherein the substituent A is a C1-C4 alkyl or C1-C4 alkoxy group; In equation (1), * represents a chiral carbon atom.

2. The chiral compound containing 2-oxazoline-8-iminequinoline as described in claim 1, characterized in that... The R 1 It is an unsubstituted or phenyl group substituted with 1-4 substituents B; The R 2 It is an unsubstituted or C1-C12 alkyl group substituted with 1-2 C1-C4 alkoxy groups; The R 3 R 4 R 5 R 6 R 7 Each is independently H or C1-C12 alkyl; The R 8 R 9 Each is independently H, an unsubstituted C1-C12 alkyl group or a C1-C4 alkyl group substituted with 1-2 C1-C4 alkoxy groups; The R 10 It is an unsubstituted or substituted C1-C12 alkyl group, or an unsubstituted or substituted aryl group A, either substituted with 1-3 substituents B.

3. The chiral compound containing 2-oxazoline-8-iminequinoline as described in claim 1, characterized in that... The R 1 It is an unsubstituted phenyl or a phenyl group substituted with 1-3 substituents B; wherein the substituents B are C1-C4 alkyl or C1-C4 alkoxy. The R 2 It is a C1-C12 alkyl group; The R 3 R 4 R 5 R 6 R 7 Each can be independently H, methyl, ethyl, isopropyl, or tert-butyl; The R 8 R 9 Each can be independently H, methyl, ethyl, isopropyl, or tert-butyl; The R 10 It is a C1-C12 alkyl, phenyl, or benzyl group.

4. The method for preparing chiral compounds containing 2-oxazoline-8-iminequinoline as described in claim 1, characterized in that... The method includes the following steps: (a) The 2-bromo-8-acylquinoline compound shown in formula (2) and the amine compound shown in formula (3) undergo a condensation reaction under the action of a catalyst to obtain the compound shown in formula (4); (b) Under nitrogen protection, the compound shown in formula (4) and the oxazoline compound shown in formula (5) were coupled together in the presence of transition metal inorganic salts, organophosphorus ligands and inorganic bases to prepare the chiral 2-oxazoline-8-iminequinoline compound shown in formula (1). (2) (3) (4) (5) R 1 ~R 10 The limitation is as described in claim 1.

5. A chiral metal complex containing a 2-oxazoline-8-iminequinoline compound, said metal complex being a combination of the chiral 2-oxazoline-8-iminequinoline compound of claim 1 and a transition metal salt ME. n The complexation reaction forms, as shown in the general formula (6) below: (6)； In equation (6), R 1 - R 10 The limitation is as described in claim 1; In formula (6), M is a transition metal such as Fe, Co, Ni, Cu, Ag, Au, Ru, Rh, Pd, Os, or Ir; E is any one of F, Cl, Br, I, CN, cyanate, tetrafluoroborate, isocyanate, carbonate, formate, acetate, propionate, methanesulfonate, trichloromethanesulfonate, phenylsulfonate, toluenesulfonate, phosphate, and hexafluorophosphate. n is the number of E, which can be 1, 2, or 3.

6. The method for preparing the chiral metal complex containing a 2-oxazoline-8-iminequinoline compound as described in claim 5, characterized in that... The method is as follows: Under nitrogen protection, the chiral compound containing 2-oxazoline-8-iminequinoline and transition metal salt ME, as shown in formula (1), n The chiral metal complex containing 2-oxazoline-8-iminequinoline compounds, as shown in formula (6), is prepared by reacting in an organic solvent for 1 to 20 hours.

7. The application of the chiral metal complex containing a 2-oxazoline-8-iminequinoline compound as described in claim 5 as a catalyst in the catalytic hydrosilylation or hydroboration reaction at carbon-carbon or carbon heteroatom double bonds.

8. The application as described in claim 7, characterized in that... The method described is as follows: a chiral metal complex containing a 2-oxazoline-8-iminequinoline compound is used to catalyze the hydroboration reaction of ketone compounds to produce alcohol compounds.

9. The application as described in claim 7, characterized in that... The method of application is as follows: the chiral metal complex containing 2-oxazoline-8-iminequinoline compounds is used to catalyze the hydrosilylation of disubstituted olefin compounds to generate alkylsilane compounds.

10. The application as described in claim 9, characterized in that... The disubstituted olefin compound is a 1,1-disubstituted olefin or a 1,2-disubstituted olefin.

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