Asymmetric hydrogenation catalytic synthesis of drugs with rare noble metal and chiral phosphine complexes

Abstract

The present invention relates to a complex of rare noble metals and chiral phosphine for asymmetric hydrogenation catalytic synthesis of drugs. The complex is composed of 1,1'-binaphthyl-2,2'-bisdiphenylphosphine, (1,5-cyclooctadiene) chlororhodium (I) dimer and fluoride-containing salt radical. The present invention also relates to a method for preparing the complex, comprising the steps of: under nitrogen protection, sequentially adding 1,1'-binaphthyl-2,2'-bisdiphenylphosphine, (1,5-cyclooctadiene) chlororhodium (I) dimer and alkanoic acid to an organic solvent, stirring evenly; adding fluoride-containing salt to the obtained mixture, continuing to stir under nitrogen protection to complete the reaction; washing with water, distilling off the solvent under reduced pressure, adding anhydrous ethanol, standing in a cold place to precipitate, and drying the collected precipitate to obtain a complex. The present invention also relates to the use of the complex for asymmetric hydrogenation catalysis to prepare chiral chiral pharmaceutical compounds. The method of the present invention has the advantages of high recovery rate.

Description

Technical Field

[0001] The present invention belongs to the field of drug synthesis, and relates to a catalyst for pharmaceutical chemical synthesis, and in particular to a catalyst for preparing pharmaceutical compounds by asymmetric hydrogenation catalysis, and in particular to preparing chiral pharmaceutical compounds. The catalyst is a complex prepared by using rare precious metals and chiral phosphines. Background Art

[0002] According to the definition of the International Union of Pure and Applied Chemistry (IUPAC), a catalyst generally refers to a substance that increases the reaction rate without changing the total standard Gibbs free energy change of the reaction. It can also be described as a substance that can increase the chemical reaction rate without changing the chemical equilibrium in a chemical reaction, and its own mass and chemical properties do not change before and after the chemical reaction. This effect is called catalysis, and the reaction involving a catalyst is called a catalytic reaction. In other words, the catalyst participates in a chemical reaction. In a total chemical reaction, the role of the catalyst is to reduce the activation energy required for the reaction to occur. In essence, it turns a relatively difficult reaction into two very easy chemical reactions (the opposite is called an inhibitor). In these two reactions, the catalyst plays the role of a reactant in the first reaction and the role of a product in the second reaction. Therefore, from the perspective of the overall reaction equation, the catalyst does not change before and after the reaction. Generally speaking, a catalyst refers to a substance that participates in the intermediate process of a chemical reaction and can selectively change the chemical reaction rate, while its own quantity and chemical properties remain basically unchanged before and after the reaction. The role of a catalyst in accelerating a chemical reaction and making the reaction reach chemical equilibrium as quickly as possible is usually called catalysis, but it does not change the equilibrium of the reaction.

[0003] According to statistics, more than 90% of industrial processes use catalysts, such as chemical, petrochemical, biochemical, environmental protection, etc. Catalysts play an extremely important role in the modern chemical industry. For example, iron catalysts are used in the production of synthetic ammonia, vanadium catalysts are used in the production of sulfuric acid, and different catalysts are used in the production of three major synthetic materials, such as the polymerization of ethylene and the production of rubber using butadiene.

[0004] Catalytic reactions involving catalysts have four basic characteristics: catalysts can only accelerate reactions that can be carried out thermodynamically; catalysts can only accelerate reactions to equilibrium and cannot change the equilibrium position of the reaction; catalysts are selective for reactions, and when the reaction may have more than one different direction, the catalyst only accelerates one of them, promoting the unity of reaction rate and selectivity; catalysts have a certain lifespan, and in the actual reaction process, the catalyst will be subjected to long-term heat and chemical action, and some irreversible physical and chemical changes will also occur. Generally speaking, catalysts have three important indicators: activity, selectivity, and stability.

[0005] There are many types of catalysts. According to their state, they can be divided into liquid catalysts and solid catalysts. According to the phase of the reaction system, they can be divided into homogeneous catalysts and heterogeneous catalysts. Homogeneous catalysts include acids, bases, soluble transition metal compounds and peroxide catalysts. Heterogeneous catalysts include solid acid catalysts, organic base catalysts, metal catalysts, metal oxide catalysts, complex catalysts, rare earth catalysts, molecular sieve catalysts, biocatalysts, nanocatalysts, etc. According to the reaction type, they can be divided into polymerization, polycondensation, esterification, acetalization, hydrogenation, dehydrogenation, oxidation, reduction, alkylation, isomerization and other catalysts. According to the size of the effect, they can be divided into main catalysts and co-catalysts.

[0006] Regarding homogeneous catalysis, the reaction that takes place when the catalyst and reactants are in the same phase without the presence of a phase boundary is called homogeneous catalysis. Catalysts that can perform homogeneous catalysis are homogeneous catalysts. Homogeneous catalysts include liquid acid, base catalysts, solid acid and base catalysts of Secosase, soluble transition metal compounds (salts and complexes), etc. Homogeneous catalysts act independently as molecules or ions, with uniform active centers, high activity and high selectivity.

[0007] Regarding heterogeneous catalysis, heterogeneous catalysts are also called non-homogeneous catalysts, which are used in reactions in different phases, that is, they are in different states from the reactants they catalyze. For example: when producing margarine, unsaturated vegetable oil and hydrogen can be converted into saturated fats through solid nickel (catalyst). Solid nickel is a heterogeneous catalyst, and the reactants catalyzed by it are liquid (vegetable oil) and gas (hydrogen). A simple heterogeneous catalytic reaction includes the reactants (or zh-ch: substrate; zh-tw: substrate) adsorbed on the surface of the catalyst, the bonds in the reactants are broken, resulting in the generation of new bonds, but because the bonds between the products and the catalyst are not strong, the products are separated from the reaction site, etc. It is now known that many different structures of adsorption and reaction occur on the surface of catalysts.

[0008] Regarding biocatalysis, enzymes are biological catalysts, which are organic substances with catalytic ability produced by plants, animals and microorganisms (mostly proteins. But a small amount of RNA also has biocatalytic function), formerly known as enzymes. The catalytic action of enzymes is also selective. For example, starch. Enzymes catalyze the hydrolysis of starch into dextrin and maltose, and proteases catalyze the hydrolysis of proteins into peptides, etc. Living organisms use them to accelerate chemical reactions in the body. Without enzymes, many chemical reactions in organisms will proceed very slowly and it will be difficult to maintain life. The working state of enzymes is optimal at a temperature of about 37°C (human body temperature). If the temperature is higher than 50°C or 60°C, the enzyme will be destroyed and can no longer work. Therefore, biological detergents that use enzymes to decompose stains on clothes are most effective when used at low temperatures. Enzymes are of great significance in physiology, medicine, agriculture, industry, etc. At present, the application of enzyme preparations is becoming more and more extensive.

[0009] Each method of manufacturing catalysts is actually composed of a series of operating units. For convenience, people use the names of the key and distinctive operating units as the names of the manufacturing methods. Traditional methods include mechanical mixing, precipitation, impregnation, solution evaporation, hot melting, leaching (leaching), ion exchange, etc. New methods currently under development include chemical bonding, fiberization, etc.

[0010] Chirality is one of the essential properties of nature. Biomacromolecules, which are important foundations of life activities, and many bioactive substances acting on receptors all have chiral characteristics. It can be seen that the asymmetry of molecules plays an important role in life processes. The biological activity of many drugs is achieved through strict chiral matching and molecular recognition between macromolecules. In fact, the enantiomers of chemical drugs containing chiral factors have significant differences in activity, metabolic processes and toxicity in the human body. Therefore, obtaining optically pure substances is an important and challenging task faced by pharmaceutical chemists. Resolving racemates and biological fermentation are classic methods for obtaining optically pure substances, but these methods have long operation steps, are not economically cost-effective, and cause pollution.

[0011] The catalytic asymmetric synthesis technology that appeared in the 1970s is also commonly known as chiral technology. It is one of the economical and scientific methods to obtain non-natural complex optically pure compounds, and has broad industrial uses and application prospects. A large amount of optically pure substances can be obtained under the action of a small amount of chiral catalysis. The key to this technology is the preparation of chiral catalysts, and the core work of preparing chiral catalysts is the selection of chiral ligands, which is the source of asymmetric induction and control of product stereochemistry by chiral catalysts.

[0012] Asymmetric catalytic hydrogenation is the earliest and most effective asymmetric reaction studied. Generally, chiral diphosphine compounds are used as ligands and complexed with transition metal rhodium or ruthenium to prepare in-situ or cationic catalysts. However, most trivalent organic phosphines are unstable and easily oxidized and hydrolyzed in the air. Therefore, water and oxygen must be excluded during synthesis, which is very troublesome to operate and difficult to prepare in large quantities. This greatly limits the application of chiral technology in industrial production. Summary of the invention

[0013] The object of the present invention is to provide a catalyst for preparing pharmaceutical compounds by asymmetric hydrogenation catalysis, wherein the catalyst is a complex prepared by using a rare noble metal and a chiral phosphine. It has been unexpectedly found that a catalyst of a rare noble metal-chiral phosphine complex that is stable in a common environment can be prepared by the method of the present invention, and the catalyst can be efficiently used for preparing pharmaceutical compounds by asymmetric hydrogenation catalysis, especially for preparing chiral pharmaceutical compounds. Another object of the present invention is to provide a method for preparing the catalyst.

[0014] To this end, the first aspect of the present invention provides a complex (which can be used as a catalyst) as shown in the following formula IV:

[0015] ,

[0016] Wherein, X is boron or phosphorus, and n is 4 or 6.

[0017] According to the complex described in the first aspect of the present invention, X is boron and n is 4, or X is phosphorus and n is 6.

[0018] According to the first aspect of the present invention, the complex has one of the following structures:

[0019] ,

[0020] ,

[0021] ,

[0022] .

[0023] The complex according to the first aspect of the present invention is prepared by a method comprising the following steps:

[0024] (i) under nitrogen protection, adding the compound of formula I, i.e. 1,1'-binaphthyl-2,2'-bisdiphenylphosphine, the compound of formula II, i.e. (1,5-cyclooctadiene)chlororhodium (I) dimer, and C4-C12 alkanoic acid to an organic solvent in sequence, and stirring evenly;

[0025] (ii) adding a compound of formula III represented by the chemical formula MXFn, i.e., a fluoride salt, to the mixture obtained in step (i), and continuing stirring under nitrogen protection to allow the reaction to proceed to completion; wherein M is selected from Li + 、Na + , K + NH 4 + , X is boron or phosphorus, and n is 4 or 6;

[0026] (iii) washing with water, distilling off the solvent under reduced pressure, adding anhydrous ethanol, leaving the mixture in a cold place to allow precipitation, and drying the collected precipitate to obtain a complex.

[0027] According to the complex described in the first aspect of the present invention, the compound of formula I is R-(+)-1,1'-binaphthyl-2,2'-bisdiphenylphosphine or S-(-)-1,1'-binaphthyl-2,2'-bisdiphenylphosphine.

[0028] According to the complex described in the first aspect of the present invention, the C4-C12 alkanoic acid is a linear monobasic alkanoic acid or a dibasic alkanoic acid.

[0029] According to the complex described in the first aspect of the present invention, the C4-C12 alkanoic acid is a linear monobasic alkanoic acid or a dibasic alkanoic acid with a carboxyl group at one or both ends.

[0030] According to the complex described in the first aspect of the present invention, the C4~C12 alkanoic acid is selected from butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, adipic acid, and azelaic acid.

[0031] According to the complex described in the first aspect of the present invention, the molar ratio of the compound of formula I to the compound of formula II is 2.5-5:1, for example, 2.5-4:1.

[0032] According to the complex described in the first aspect of the present invention, the molar ratio of C4-C12 alkanoic acid to the compound of formula II is 0.1-0.6:1, for example, 0.1-0.5:1.

[0033] According to the complex described in the first aspect of the present invention, the molar ratio of the fluorine-containing salt represented by the compound of formula III to the compound of formula II is 4-8:1, for example, 5-7:1.

[0034] According to the complex described in the first aspect of the present invention, the organic solvent in step (i) is selected from dichloromethane, trichloromethane, dichloroethane, tetrachloroethane, etc., and it is known that these organic solvents are commonly used and feasible in similar reactions in the field. In the present invention, the preferred organic solvent is dichloromethane. In one embodiment, the amount of the organic solvent used is 20 to 50 mL, for example 20 to 40 mL, per 1 mmol of the compound of formula II.

[0035] According to the complex described in the first aspect of the present invention, in step (i), the material is stirred under nitrogen protection for 10 to 30 minutes, for example, 10 to 20 minutes.

[0036] According to the complex of the first aspect of the present invention, in step (ii), the compound of formula III is preliminarily dissolved in water. The amount of water used is generally as small as possible, for example, 10-30 mL of water can be used to dissolve every 6 mmol of the compound of formula III.

[0037] According to the complex described in the first aspect of the present invention, in step (ii), the material is stirred under nitrogen protection for 10 to 30 min, such as 30 to 60 min, such as 40 to 50 min, such as 45 min.

[0038] According to the complex described in the first aspect of the present invention, in step (iii), the complex is washed with water for 1 to 5 times, for example, 2 to 4 times, for example, 3 times.

[0039] According to the complex described in the first aspect of the present invention, in step (iii), the amount of anhydrous ethanol added is 50-100 mL, such as 60-90 mL, such as 70-90 mL, such as 80 mL, per 1 mmol of the compound of formula II.

[0040] According to the complex described in the first aspect of the present invention, in step (iii), the material is allowed to stand at -10~0°C, for example, -5°C, for 5~15h, for example, 6~12h, for example, 7~9h, for example, 8h.

[0041] According to the complex described in the first aspect of the present invention, in step (iii), the precipitate is collected by centrifugation and the supernatant is discarded.

[0042] The complex according to the first aspect of the present invention is prepared according to a method comprising the following steps:

[0043] (i) under nitrogen protection, 3 mmol of the compound of formula I, i.e., 1,1'-binaphthyl-2,2'-bisdiphenylphosphine, 1 mmol of the compound of formula II, i.e., (1,5-cyclooctadiene)chlororhodium (I) dimer, and 0.2 mmol of C4-C12 alkanoic acid were added to 30 mL of dichloromethane in a round-bottom flask in sequence, and stirred for 15 min;

[0044] (ii) To the mixture obtained in step (i), add 6 mmol of the hexafluorophosphate or tetrafluoroborate of the compound of formula III pre-dissolved in 15 mL of water, continue stirring for 45 min under nitrogen protection, wash with water 3 times, evaporate the solvent under reduced pressure, add 80 mL of anhydrous ethanol, let stand at -5°C for 8 h, centrifuge, discard the supernatant, harvest the precipitate, and dry to obtain a complex.

[0045] Further, the second aspect of the present invention provides a method for preparing a complex (which can be used as a catalyst) as shown in the following formula IV:

[0046] ,

[0047] Wherein, X is boron or phosphorus, n is 4 or 6,

[0048] The method comprises the following steps:

[0049] (i) under nitrogen protection, adding the compound of formula I, i.e. 1,1'-binaphthyl-2,2'-bisdiphenylphosphine, the compound of formula II, i.e. (1,5-cyclooctadiene)chlororhodium (I) dimer, and C4-C12 alkanoic acid to an organic solvent in sequence, and stirring evenly;

[0050] (ii) adding a compound of formula III represented by the chemical formula MXFn, i.e., a fluoride salt, to the mixture obtained in step (i), and continuing stirring under nitrogen protection to allow the reaction to proceed to completion; wherein M is selected from Li+ 、Na + , K + NH 4 + , X is boron or phosphorus, and n is 4 or 6;

[0051] (iii) washing with water, distilling off the solvent under reduced pressure, adding anhydrous ethanol, leaving the mixture in a cold place to allow precipitation, and drying the collected precipitate to obtain a complex.

[0052] According to the method of the second aspect of the present invention, X is boron and n is 4, or X is phosphorus and n is 6.

[0053] According to the method of the second aspect of the present invention, the compound of formula IV has one of the following structures:

[0054] ,

[0055] ,

[0056] ,

[0057] .

[0058] According to the method of the second aspect of the present invention, the compound of formula I is R-(+)-1,1'-binaphthyl-2,2'-bisdiphenylphosphine or S-(-)-1,1'-binaphthyl-2,2'-bisdiphenylphosphine.

[0059] According to the method of the second aspect of the present invention, the C4-C12 alkanoic acid is a linear monobasic alkanoic acid or a dibasic alkanoic acid.

[0060] According to the method of the second aspect of the present invention, the C4-C12 alkanoic acid is a linear monobasic alkanoic acid or a dibasic alkanoic acid having a carboxyl group at one or both ends.

[0061] According to the method of the second aspect of the present invention, the C4~C12 alkanoic acid is selected from butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, adipic acid, and azelaic acid.

[0062] According to the method of the second aspect of the present invention, the molar ratio of the compound of formula I to the compound of formula II is 2.5-5:1, for example 2.5-4:1.

[0063] According to the method of the second aspect of the present invention, the molar ratio of C4-C12 alkanoic acid to the compound of formula II is 0.1-0.6:1, for example 0.1-0.5:1.

[0064] According to the method of the second aspect of the present invention, the molar ratio of the fluorine-containing salt represented by the compound of formula III to the compound of formula II is 4-8:1, for example, 5-7:1.

[0065] According to the method of the second aspect of the present invention, the organic solvent in step (i) is selected from dichloromethane, trichloromethane, dichloroethane, tetrachloroethane, etc., and it is known that these organic solvents are commonly used and feasible in similar reactions in the field. In the present invention, the preferred organic solvent is dichloromethane. In one embodiment, the amount of the organic solvent used is 20 to 50 mL, for example, 20 to 40 mL, per 1 mmol of the compound of formula II.

[0066] According to the method of the second aspect of the present invention, in step (i), the material is stirred under nitrogen protection for 10 to 30 minutes, for example, 10 to 20 minutes.

[0067] According to the method of the second aspect of the present invention, in step (ii), the compound of formula III is pre-dissolved in water. The amount of water used is generally as small as possible, for example, 10 to 30 mL of water can be used to dissolve every 6 mmol of the compound of formula III.

[0068] According to the method of the second aspect of the present invention, in step (ii), the material is stirred under nitrogen protection for 10 to 30 minutes, such as 30 to 60 minutes, such as 40 to 50 minutes, such as 45 minutes.

[0069] According to the method of the second aspect of the present invention, in step (iii), washing with water is performed 1 to 5 times, for example, 2 to 4 times, for example, 3 times.

[0070] According to the method of the second aspect of the present invention, in step (iii), the amount of anhydrous ethanol added per 1 mmol of compound of formula II is 50-100 mL, for example 60-90 mL, for example 70-90 mL, for example 80 mL.

[0071] According to the method of the second aspect of the present invention, in step (iii), the material is left to stand at -10 to 0°C, for example -5°C, for 5 to 15 hours, for example 6 to 12 hours, for example 7 to 9 hours, for example 8 hours.

[0072] According to the method of the second aspect of the present invention, in step (iii), the precipitate is collected by centrifugation and the supernatant is discarded.

[0073] The method according to the second aspect of the present invention comprises the following steps:

[0074] (i) under nitrogen protection, 3 mmol of the compound of formula I, i.e., 1,1'-binaphthyl-2,2'-bisdiphenylphosphine, 1 mmol of the compound of formula II, i.e., (1,5-cyclooctadiene)chlororhodium (I) dimer, and 0.2 mmol of C4-C12 alkanoic acid were added to 30 mL of dichloromethane in a round-bottom flask in sequence, and stirred for 15 min;

[0075] (ii) To the mixture obtained in step (i), add 6 mmol of the hexafluorophosphate or tetrafluoroborate of the compound of formula III pre-dissolved in 15 mL of water, continue stirring for 45 min under nitrogen protection, wash with water 3 times, evaporate the solvent under reduced pressure, add 80 mL of anhydrous ethanol, let stand at -5°C for 8 h, centrifuge, discard the supernatant, harvest the precipitate, and dry to obtain a complex.

[0076] Any embodiment of any aspect of the present invention can be combined with any other embodiment, as long as such combination does not cause contradiction. The present invention is further described below.

[0077] In the present invention, when referring to %, unless otherwise specified, for the case of a solid solute and a liquid solvent, it is a weight / volume percentage, and for the case of a solid distributed in a solid, it is a weight / weight percentage.

[0078] As we all know, rhodium (Rhodium, element symbol Rh) is a rare silvery white, hard platinum precious metal element, with an atomic number of 45 and an atomic weight of 102.9. It is a transition metal element of the fifth period VIII group in the periodic table. The density of rhodium is as high as 12.41 g / cm3, which is more than twice that of platinum. The hardness is 4~4.5 and the melting point is as high as 1966℃. Rhodium has strong corrosion resistance. It is not corroded by most acids and alkalis. Rhodium has high reflectivity. Rhodium metal usually does not form oxides. Molten rhodium absorbs oxygen, but releases it during the solidification process. The melting point of rhodium is higher than that of platinum and the density is lower than that of platinum. Rhodium is insoluble in most acids. It is completely insoluble in nitric acid and slightly soluble in aqua regia. Rhodium can react chemically with hot concentrated sulfuric acid, hot hydrobromic acid, sodium hypochlorite and free halogens at 200-600℃. It does not react with many molten metals, such as gold, silver, sodium and potassium, and molten alkalis. Platinum group metals have a high melting point, high strength, stable electrothermal properties, high resistance to electric spark erosion, excellent corrosion resistance, strong high-temperature antioxidant properties, and good catalytic activity. They are widely used in automobile exhaust purification, chemical industry, aerospace, glass fiber, electronics and electrical industries. Although the amount used is small, they play a key role and are known as "industrial vitamins."

[0079] (1,5-cyclooctadiene) rhodium chloride (I) dimer, also known as rhodium chloride COD, bis (1,5-cyclooctadiene rhodium chloride), etc., its English name is: Chloro (1,5-cyclooctadiene) rhodium (I) dimer, or also known as Rhodiumchloro (cycloocta-1,5-diene) dimer, CAS No. 12092-47-6, molecular formula C16H24Cl2Rh2, molecular weight 493.08, its chemical structure is:

[0080] Compound of formula II.

[0081] The melting point of (1,5-cyclooctadiene)chlororhodium (I) dimer is 243°C (dec.) (lit.), soluble in chloroform, dichloromethane and methanol, and slightly soluble in most common solvents. (1,5-cyclooctadiene)chlororhodium (I) dimer is orange to orange-brown crystals or crystalline powders, with a water solubility of 1.56 g / L (20°C). (1,5-cyclooctadiene)chlororhodium (I) dimer is often used as a metal ligand for the synthesis of catalytic reactions, such as catalysts for the reaction of 1,3-dienes and activated hydrocarbons and the preparation of chiral complexes, typically used for coupling reactions, asymmetric hydrogenation reactions, and hydroboration reactions.

[0082] The following formula shows 1,1'-binaphthyl-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, with a molecular formula of C44H32P2, a molecular weight of 622.69, and a chemical structure:

[0083] Compounds of formula I.

[0084] 1,1'-Binaphthyl-2,2'-bis(diphenylphosphine) usually has two isomers, namely:

[0085] R-(+)-1,1'-binaphthyl-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, CAS No. 76189-55-4, chemical structure:

[0086] ;as well as,

[0087] S-(-)-1,1'-binaphthyl-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, CAS No. 76189-56-5, chemical structure:

[0088] .

[0089] The melting points of the above two types of binaphthyl bis(diphenylphosphine) are both 283-286°C (lit.), and the boiling points are both 724.3±55.0°C. The specific rotation of the R-(+)-configuration is [α]20 / D=240º(c=0.3, toluene) or [α]20 / D=222°(c=0.5%, benzene), and the refractive index is 235°(c=0.3, toluene), and the specific rotation of the S-(-)-configuration is [α]20 / D=-240º(c=0.3, toluene) or [α]20 / D=-222°(c=0.5%, benzene), and the refractive index is -235°(c=0.3, toluene). 1,1'-binaphthyl-2,2'-bis(diphenylphosphine) can be stored at room temperature.

[0090] R-(+)-1,1'-binaphthyl-2,2'-bisdiphenylphosphine and S-(-)-1,1'-binaphthyl-2,2'-bisdiphenylphosphine are organophosphites that can be used as effective ligands for transition metal-catalyzed asymmetric reactions (including hydrogenation and disilylation). Their rhodium derivatives can be used as highly selective homogeneous catalysts for the reduction of aryl ketones, β-ketoesters and α-aminoketones, as well as for the asymmetric hydrogenation and hydroformylation of olefins, asymmetric Heck reactions and asymmetric isomerization of allyl groups. It is known that the Ag(I) complex of 1,1'-binaphthyl-2,2'-bisdiphenylphosphine can be used to catalyze the asymmetric aldol reaction between alkenyl trichloroacetate and aldehydes, and can also be used to catalyze the asymmetric heterogeneous Diels-Alder reaction of azo compounds. In addition, 1,1'-binaphthyl-2,2'-bis-diphenylphosphine can also be used as a ligand in palladium-catalyzed asymmetric tandem Heck reactions. This carbon anion capture process can synthesize tricyclic sesquiterpenes. 1,1'-binaphthyl-2,2'-bis-diphenylphosphine can also be used in ruthenium-catalyzed asymmetric hydrogenation of α,β-unsaturated acids. 1,1'-binaphthyl-2,2'-bis-diphenylphosphine is a C2-axial chiral diphosphine compound used as an inducer of chiral reactions; as an effective ligand in transition metal-catalyzed asymmetric reactions, including hydroxylation reactions and disilylation reactions; 1,1'-binaphthyl-2,2'-bis-diphenylphosphine is also used in asymmetric hydroxylation reactions and hydroxyl formation reactions of olefins, asymmetric Heck reactions, and asymmetric isomerization reactions of allyl groups.

[0091] The method of the present invention exhibits excellent technical effects as described herein above and below. DETAILED DESCRIPTION

[0092] The present invention can be further described by the following examples, however, the scope of the present invention is not limited to the following examples. It will be appreciated by those skilled in the art that various changes and modifications may be made to the present invention without departing from the spirit and scope of the present invention. The present invention provides general and / or specific descriptions of the materials and test methods used in the test. Although many materials and operating methods used to achieve the purpose of the present invention are well known in the art, the present invention is still described in as much detail as possible here.

[0093] In the following experiments of the present invention, the feeding amount of each material can be proportionally enlarged or reduced according to specific needs. In addition, various materials used in the present invention can be easily obtained through commercial channels, for example, it is easy to find suppliers of various materials from https: / / www.chemicalbook.com / .

[0094] Example 1: Preparation of rare noble metal and chiral phosphine complex catalyst

[0095] In this embodiment, a catalyst of a rare noble metal and a chiral phosphine complex is prepared according to the following scheme (other examples can also be prepared by referring to similar schemes):

[0096] .

[0097] Under nitrogen protection, 3 mmol of R-(+)-1,1'-binaphthyl-2,2'-bisdiphenylphosphine (compound of formula I), 1 mmol of (1,5-cyclooctadiene)chlororhodium (I) dimer (compound of formula II) and 0.2 mmol of hexanoic acid were added to 30 mL of dichloromethane in a round-bottom flask in sequence, and stirred for 15 min; then 6 mmol of KPF6 (compound of formula III) pre-dissolved in 15 mL of water was added to the reaction solution, and stirring was continued for 45 min under nitrogen protection, washed with water 3 times, the solvent was evaporated under reduced pressure, 80 mL of anhydrous ethanol was added, and the mixture was allowed to stand at -5°C for 8 h, centrifuged, the supernatant was discarded, the light yellow precipitate was harvested, and dried to obtain 946 mg of the complex of binaphthyl configuration shown in the following formula IVa:

[0098] ;

[0099] Molecular formula C52H44F6P3Rh, molecular weight Mr=978.7; elemental analysis results (%): C63.82, H4.54, F11.63, P9.49, Rh (%) = 10.36%, the elemental analysis results are consistent with the theoretical value; purity 98.47%, the recovery rate calculated by precious metals is 95.1%; 1 H NMR (400 MHz, CDCl 3) δ:7.89(d, J=8.6Hz, 2H), 7.82(d, J=8.0Hz, 2H), 7.46(d, J=8.0Hz, 2H), 7.36(t, J=7.1Hz, 2H), 7.21-7.05(m, 20H), 6.93(t, J=6.7Hz, 2H), 6.84(d, J=8.3Hz, 2H), 5.20~5.34(m, 4H), 2.00~2.09(m, 8H); 31 P NMR ((CD 3 ) 2 CO, 162MHz): 24.46(d, J(P-Rh)=138.5Hz); 27.64(d, J(P-Rh)=141.5Hz) ppm; IR(solid)v max 3048.4, 2926.2, 1702.4, 1433.5, 1238.4, 813.8.

[0100] In the present invention, the hexanoic acid and the butanoic acid, heptanoic acid, nonanoic acid, etc. used herein can be collectively referred to as alkanoic acid. Unless otherwise specified, the alkanoic acid is a linear monobasic alkanoic acid or a dibasic alkanoic acid with a carboxyl group at one or both ends. As described herein, the preferred alkanoic acid is a monobasic alkanoic acid or a dibasic alkanoic acid with a chain length of C4 to C12.

[0101] Test Example 1: Determination of the rhodium content in the complex

[0102] This test example refers to the prior art, such as the method described in GB1485-79, etc. to determine the rhodium content in the complex, and the reagents used are all routinely available to those skilled in the art.

[0103] Samples and reagents: The test sample (complex of formula IV obtained in Example 1) was vacuum dried at 75°C for 4 hours before testing; the hexaamminecobalt nitrate washing solution was a 0.05% hexaamminecobalt nitrate aqueous solution; the hexaamminecobalt nitrate saturated solution (as a precipitant solution) was weighed 17 g of crystalline hexaamminecobalt nitrate, added 300 mL of deionized water, heated to dissolve, filtered with a rapid filter paper, and then diluted with high-purity water to 1000 mL.

[0104] Determination method:

[0105] Accurately weigh 0.5g (w, accurate to 0.1mg) of the test sample, place it in a conical beaker, add 15mL of 98% w / v concentrated sulfuric acid, cover with a watch glass, place the conical beaker on a hot plate with asbestos wire mesh, and boil slightly for 150 minutes. Remove the watch glass, continue heating until the residual liquid is 2ml, repeatedly add 65% w / v concentrated nitric acid until no more white smoke, at which point the residual liquid should be transparent dark red and contain no black, red or white precipitates. Add 36% w / v hydrochloric acid to the residual liquid, continue heating until no more red steam (the amount of hydrochloric acid is about 2ml), at which point the residual liquid should be a darker rose red. After cooling to room temperature, add 300ml of deionized water to the residual liquid, at which point the solution should be rose red. If the solution becomes turbid or white, red, or black precipitates appear, the sample should be weighed and redone.

[0106] The solution was heated to 60°C, sodium nitrite (about 6 g) was added in portions until the color of the solution faded, heating and boiling were continued, saturated hexaamminecobalt nitrate solution was added dropwise with vigorous stirring, and heating and stirring were continued (a large amount of yellow precipitate was precipitated) until no more yellow precipitate was precipitated (the amount of saturated hexaamminecobalt nitrate solution was about 25 ml), and a slight boil was maintained for 10 minutes, and heating was stopped. The precipitate was aged at the residual temperature for 20 minutes; after the beaker was cooled to room temperature, it was filtered with a No. 4 glass sand crucible that had been cleaned, vacuum dried and weighed to constant weight (w2) in advance, and the precipitate adhering to the beaker and the wall was completely transferred into the crucible with a glass rod with a rubber head, and the precipitate was washed twice with hexaamminecobalt nitrate washing solution, washed three times with anhydrous ethanol, and washed once with ether.

[0107] Place the crucible in a vacuum drying oven, vacuum dry it at room temperature for 1 hour, then weigh it, and then vacuum dry it for 0.5 hour, then weigh it (w3, the sum of the weight of the precipitate w1 and the weight of the crucible w2), and repeat this operation until the difference between the two weighings is ≤0.3mg. The percentage content of rhodium Rh (%) is calculated as follows:

[0108] ,

[0109] Wherein, w1 is the precipitate weight (mg), w2 is the crucible weight (mg), w is the sample weight (mg), and 0.19054 is the conversion coefficient of rhodium complex to rhodium.

[0110] The Rh (%) calculated using the above formula is the absolute percentage content of metal rhodium in the complex. After measurement, the Rh (%) of the complex obtained in Example 1 is 10.36%, and the theoretical content of rhodium in the complex shown in Formula IV is 10.52%, indicating that the purity of the obtained complex is as high as 98.47% (10.36÷10.52).

[0111] The rhodium content and purity of the complexes obtained in other examples of the present invention can also be determined using the method of Test Example 1.

[0112] Example 2: Preparation of rare noble metal and chiral phosphine complex catalyst

[0113] The catalyst of rare noble metal and chiral phosphine complex was prepared by the method of reference example 1:

[0114] Under nitrogen protection, 3 mmol of S-(-)-1,1'-binaphthyl-2,2'-bisdiphenylphosphine (compound of formula I), 1 mmol of (1,5-cyclooctadiene)chlororhodium (I) dimer (compound of formula II) and 0.2 mmol of hexanoic acid were added in sequence to 30 mL of dichloromethane in a round-bottom flask, and stirred for 15 min; then 6 mmol of KPF6 (compound of formula III) pre-dissolved in 15 mL of water was added to the reaction solution, and stirring was continued for 45 min under nitrogen protection, washed with water 3 times, the solvent was evaporated under reduced pressure, 80 mL of anhydrous ethanol was added, and the mixture was allowed to stand at -5°C for 8 h, centrifuged, the supernatant was discarded, the light yellow precipitate was harvested, and dried to obtain a complex of binaphthyl configuration shown in the following formula IVa, and the elemental analysis results were consistent with the theoretical values, the product purity was 97.73%, and the recovery rate was 95.8%.

[0115] .

[0116] Example 3: Preparation of rare noble metal and chiral phosphine complex catalyst

[0117] The catalyst of rare noble metal and chiral phosphine complex was prepared by the method of reference example 1:

[0118] Under nitrogen protection, 3 mmol of R-(+)-1,1'-binaphthyl-2,2'-bisdiphenylphosphine (compound of formula I), 1 mmol of (1,5-cyclooctadiene)chlororhodium (I) dimer (compound of formula II) and 0.2 mmol of butyric acid were added in sequence to 30 mL of dichloromethane in a round-bottom flask, and stirred for 15 min; then 6 mmol of KPF6 (compound of formula III) pre-dissolved in 15 mL of water was added to the reaction solution, and stirring was continued for 45 min under nitrogen protection, washed with water 3 times, the solvent was evaporated under reduced pressure, 80 mL of anhydrous ethanol was added, and the mixture was allowed to stand at -5°C for 8 h, centrifuged, the supernatant was discarded, the light yellow precipitate was harvested, and dried to obtain a complex of formula IVa with a corresponding binaphthyl configuration. The elemental analysis results were consistent with the theoretical values, the product purity was 98.25%, and the recovery rate was 91.7%.

[0119] Example 4: Preparation of rare noble metal and chiral phosphine complex catalyst

[0120] The catalyst of rare noble metal and chiral phosphine complex was prepared by the method of reference example 1:

[0121] Under nitrogen protection, 3 mmol of S-(-)-1,1'-binaphthyl-2,2'-bisdiphenylphosphine (compound of formula I), 1 mmol of (1,5-cyclooctadiene)chlororhodium (I) dimer (compound of formula II) and 0.2 mmol of butyric acid were added to 30 mL of dichloromethane in a round-bottom flask in sequence, and stirred for 15 min; then 6 mmol of KPF6 (compound of formula III) pre-dissolved in 15 mL of water was added to the reaction solution, and stirring was continued for 45 min under nitrogen protection, washed with water 3 times, the solvent was evaporated under reduced pressure, 80 mL of anhydrous ethanol was added, and the mixture was allowed to stand at -5°C for 8 h, centrifuged, the supernatant was discarded, the light yellow precipitate was harvested, and dried to obtain a complex of formula IVa with a corresponding binaphthyl configuration. The elemental analysis results were consistent with the theoretical values, the product purity was 97.64%, and the recovery rate was 91.2%.

[0122] Example 5: Preparation of rare noble metal and chiral phosphine complex catalyst

[0123] The catalyst of rare noble metal and chiral phosphine complex was prepared by the method of reference example 1:

[0124] Under nitrogen protection, 3 mmol of R-(+)-1,1'-binaphthyl-2,2'-bisdiphenylphosphine (compound of formula I), 1 mmol of (1,5-cyclooctadiene)chlororhodium (I) dimer (compound of formula II) and 0.2 mmol of octanoic acid were added to 30 mL of dichloromethane in a round-bottom flask in sequence, and stirred for 15 min; then 6 mmol of KPF6 (compound of formula III) pre-dissolved in 15 mL of water was added to the reaction solution, and stirring was continued for 45 min under nitrogen protection, washed with water 3 times, the solvent was evaporated under reduced pressure, 80 mL of anhydrous ethanol was added, and the mixture was allowed to stand at -5°C for 8 h, centrifuged, the supernatant was discarded, the light yellow precipitate was harvested, and dried to obtain a complex of formula IVa with a corresponding binaphthyl configuration. The elemental analysis results were consistent with the theoretical values, the product purity was 98.14%, and the recovery rate was 96.1%.

[0125] Example 6: Preparation of rare noble metal and chiral phosphine complex catalyst

[0126] The catalyst of rare noble metal and chiral phosphine complex was prepared by the method of reference example 1:

[0127] Under nitrogen protection, 3 mmol of S-(-)-1,1'-binaphthyl-2,2'-bisdiphenylphosphine (compound of formula I), 1 mmol of (1,5-cyclooctadiene)chlororhodium (I) dimer (compound of formula II) and 0.2 mmol of octanoic acid were added to 30 mL of dichloromethane in a round-bottom flask in sequence, and stirred for 15 min; then 6 mmol of KPF6 (compound of formula III) pre-dissolved in 15 mL of water was added to the reaction solution, and stirring was continued for 45 min under nitrogen protection, washed with water 3 times, the solvent was evaporated under reduced pressure, 80 mL of anhydrous ethanol was added, and the mixture was allowed to stand at -5°C for 8 h, centrifuged, the supernatant was discarded, the light yellow precipitate was harvested, and dried to obtain a complex of formula IVa with a corresponding binaphthyl configuration. The elemental analysis results were consistent with the theoretical values, the product purity was 98.06%, and the recovery rate was 95.6%.

[0128] Example 7: Preparation of rare noble metal and chiral phosphine complex catalyst

[0129] The catalyst of rare noble metal and chiral phosphine complex was prepared by the method of reference example 1:

[0130] Under nitrogen protection, 3 mmol of R-(+)-1,1'-binaphthyl-2,2'-bisdiphenylphosphine (compound of formula I), 1 mmol of (1,5-cyclooctadiene)chlororhodium (I) dimer (compound of formula II) and 0.2 mmol of decanoic acid were added to 30 mL of dichloromethane in a round-bottom flask in sequence, and stirred for 15 min; then 6 mmol of KPF6 (compound of formula III) pre-dissolved in 15 mL of water was added to the reaction solution, and stirring was continued for 45 min under nitrogen protection, washed with water 3 times, the solvent was evaporated under reduced pressure, 80 mL of anhydrous ethanol was added, and the mixture was allowed to stand at -5°C for 8 h, centrifuged, the supernatant was discarded, the light yellow precipitate was harvested, and dried to obtain a complex of formula IVa with a corresponding binaphthyl configuration. The elemental analysis results were consistent with the theoretical values, the product purity was 97.61%, and the recovery rate was 95.6%.

[0131] Example 8: Preparation of rare noble metal and chiral phosphine complex catalyst

[0132] The catalyst of rare noble metal and chiral phosphine complex was prepared by the method of reference example 1:

[0133] Under nitrogen protection, 3 mmol of S-(-)-1,1'-binaphthyl-2,2'-bisdiphenylphosphine (compound of formula I), 1 mmol of (1,5-cyclooctadiene)chlororhodium (I) dimer (compound of formula II) and 0.2 mmol of decanoic acid were added to 30 mL of dichloromethane in a round-bottom flask in sequence, and stirred for 15 min; then 6 mmol of KPF6 (compound of formula III) pre-dissolved in 15 mL of water was added to the reaction solution, and stirring was continued for 45 min under nitrogen protection, washed with water 3 times, the solvent was evaporated under reduced pressure, 80 mL of anhydrous ethanol was added, and the mixture was allowed to stand at -5°C for 8 h, centrifuged, the supernatant was discarded, the light yellow precipitate was harvested, and dried to obtain a complex of formula IVa with a corresponding binaphthyl configuration. The elemental analysis results were consistent with the theoretical values, the product purity was 97.37%, and the recovery rate was 95.4%.

[0134] Example 9: Preparation of rare noble metal and chiral phosphine complex catalyst

[0135] The catalyst of rare noble metal and chiral phosphine complex was prepared by the method of reference example 1:

[0136] Under nitrogen protection, 3 mmol of R-(+)-1,1'-binaphthyl-2,2'-bisdiphenylphosphine (compound of formula I), 1 mmol of (1,5-cyclooctadiene)chlororhodium (I) dimer (compound of formula II) and 0.2 mmol of nonanoic acid were added in sequence to 30 mL of dichloromethane in a round-bottom flask, and stirred for 15 min; then 6 mmol of KPF6 (compound of formula III) pre-dissolved in 15 mL of water was added to the reaction solution, and stirring was continued for 45 min under nitrogen protection, washed with water 3 times, the solvent was evaporated under reduced pressure, 80 mL of anhydrous ethanol was added, and the mixture was allowed to stand at -5°C for 8 h, centrifuged, the supernatant was discarded, the light yellow precipitate was harvested, and dried to obtain a complex of formula IVa with a corresponding binaphthyl configuration. The elemental analysis results were consistent with the theoretical values, the product purity was 98.03%, and the recovery rate was 96.2%.

[0137] Example 10: Preparation of rare noble metal and chiral phosphine complex catalyst

[0138] The catalyst of rare noble metal and chiral phosphine complex was prepared by the method of reference example 1:

[0139] Under nitrogen protection, 3 mmol of S-(-)-1,1'-binaphthyl-2,2'-bisdiphenylphosphine (compound of formula I), 1 mmol of (1,5-cyclooctadiene)chlororhodium (I) dimer (compound of formula II) and 0.2 mmol of nonanoic acid were added in sequence to 30 mL of dichloromethane in a round-bottom flask, and stirred for 15 min; then 6 mmol of KPF6 (compound of formula III) pre-dissolved in 15 mL of water was added to the reaction solution, and stirring was continued for 45 min under nitrogen protection, washed with water 3 times, the solvent was evaporated under reduced pressure, 80 mL of anhydrous ethanol was added, and the mixture was allowed to stand at -5°C for 8 h, centrifuged, the supernatant was discarded, the light yellow precipitate was harvested, and dried to obtain a complex of formula IVa with a corresponding binaphthyl configuration. The elemental analysis results were consistent with the theoretical values, the product purity was 97.87%, and the recovery rate was 95.5%.

[0140] Example 11: Preparation of rare noble metal and chiral phosphine complex catalyst

[0141] The catalyst of rare noble metal and chiral phosphine complex was prepared by the method of reference example 1:

[0142] Under nitrogen protection, 3 mmol of R-(+)-1,1'-binaphthyl-2,2'-bisdiphenylphosphine (compound of formula I), 1 mmol of (1,5-cyclooctadiene)chlororhodium (I) dimer (compound of formula II) and 0.2 mmol of heptanoic acid were added to 30 mL of dichloromethane in a round-bottom flask in sequence, and stirred for 15 min; then 6 mmol of KPF6 (compound of formula III) pre-dissolved in 15 mL of water was added to the reaction solution, and stirring was continued for 45 min under nitrogen protection, washed with water 3 times, the solvent was evaporated under reduced pressure, 80 mL of anhydrous ethanol was added, and the mixture was allowed to stand at -5°C for 8 h, centrifuged, the supernatant was discarded, the light yellow precipitate was harvested, and dried to obtain a complex of formula IVa with a corresponding binaphthyl configuration. The elemental analysis results were consistent with the theoretical values, the product purity was 98.27%, and the recovery rate was 96.0%.

[0143] Example 12: Preparation of rare noble metal and chiral phosphine complex catalyst

[0144] The catalyst of rare noble metal and chiral phosphine complex was prepared by the method of reference example 1:

[0145] Under nitrogen protection, 3 mmol of S-(-)-1,1'-binaphthyl-2,2'-bisdiphenylphosphine (compound of formula I), 1 mmol of (1,5-cyclooctadiene)chlororhodium (I) dimer (compound of formula II) and 0.2 mmol of heptanoic acid were added in sequence to 30 mL of dichloromethane in a round-bottom flask, and stirred for 15 min; then 6 mmol of KPF6 (compound of formula III) pre-dissolved in 15 mL of water was added to the reaction solution, and stirring was continued for 45 min under nitrogen protection, washed with water 3 times, the solvent was evaporated under reduced pressure, 80 mL of anhydrous ethanol was added, and the mixture was allowed to stand at -5°C for 8 h, centrifuged, the supernatant was discarded, the light yellow precipitate was harvested, and dried to obtain a complex of formula IVa with a corresponding binaphthyl configuration. The elemental analysis results were consistent with the theoretical values, the product purity was 97.58%, and the recovery rate was 95.8%.

[0146] Example 13: Preparation of rare noble metal and chiral phosphine complex catalyst

[0147] The catalyst of rare noble metal and chiral phosphine complex was prepared by the method of reference example 1:

[0148] Under nitrogen protection, 3 mmol of R-(+)-1,1'-binaphthyl-2,2'-bisdiphenylphosphine (compound of formula I), 1 mmol of (1,5-cyclooctadiene)chlororhodium (I) dimer (compound of formula II) and 0.2 mmol of valeric acid were added to 30 mL of dichloromethane in a round-bottom flask in sequence, and stirred for 15 min; then 6 mmol of KPF6 (compound of formula III) pre-dissolved in 15 mL of water was added to the reaction solution, and stirring was continued for 45 min under nitrogen protection, washed with water 3 times, the solvent was evaporated under reduced pressure, 80 mL of anhydrous ethanol was added, and the mixture was allowed to stand at -5°C for 8 h, centrifuged, the supernatant was discarded, the light yellow precipitate was harvested, and dried to obtain a complex of formula IVa with a corresponding binaphthyl configuration. The elemental analysis results were consistent with the theoretical values, the product purity was 97.03%, and the recovery rate was 93.8%.

[0149] Example 14: Preparation of rare noble metal and chiral phosphine complex catalyst

[0150] The catalyst of rare noble metal and chiral phosphine complex was prepared by the method of reference example 1:

[0151] Under nitrogen protection, 3 mmol of S-(-)-1,1'-binaphthyl-2,2'-bisdiphenylphosphine (compound of formula I), 1 mmol of (1,5-cyclooctadiene)chlororhodium (I) dimer (compound of formula II) and 0.2 mmol of valeric acid were added to 30 mL of dichloromethane in a round-bottom flask in sequence, and stirred for 15 min; then 6 mmol of KPF6 (compound of formula III) pre-dissolved in 15 mL of water was added to the reaction solution, and stirring was continued for 45 min under nitrogen protection, washed with water 3 times, the solvent was evaporated under reduced pressure, 80 mL of anhydrous ethanol was added, and the mixture was allowed to stand at -5°C for 8 h, centrifuged, the supernatant was discarded, the light yellow precipitate was harvested, and dried to obtain a complex of formula IVa with a corresponding binaphthyl configuration. The elemental analysis results were consistent with the theoretical values, the product purity was 97.26%, and the recovery rate was 93.5%.

[0152] Example 15: Preparation of rare noble metal and chiral phosphine complex catalyst

[0153] The catalyst of rare noble metal and chiral phosphine complex was prepared by the method of reference example 1:

[0154] Under nitrogen protection, 3 mmol of R-(+)-1,1'-binaphthyl-2,2'-bisdiphenylphosphine (compound of formula I), 1 mmol of (1,5-cyclooctadiene)chlororhodium (I) dimer (compound of formula II) and 0.12 mmol of azelaic acid were added in sequence to 30 mL of dichloromethane in a round-bottom flask, and stirred for 15 min; then 6 mmol of KPF6 (compound of formula III) pre-dissolved in 15 mL of water was added to the reaction solution, and stirring was continued for 45 min under nitrogen protection. The mixture was washed with water 3 times, the solvent was evaporated under reduced pressure, 80 mL of anhydrous ethanol was added, the mixture was allowed to stand at -5°C for 8 h, centrifuged, the supernatant was discarded, the light yellow precipitate was harvested, and dried to obtain a complex of formula IVa with a corresponding binaphthyl configuration. The elemental analysis results were consistent with the theoretical values, the product purity was 97.94%, and the recovery rate was 96.0%.

[0155] Example 16: Preparation of rare noble metal and chiral phosphine complex catalyst

[0156] The catalyst of rare noble metal and chiral phosphine complex was prepared by the method of reference example 1:

[0157] Under nitrogen protection, 3 mmol of S-(-)-1,1'-binaphthyl-2,2'-bisdiphenylphosphine (compound of formula I), 1 mmol of (1,5-cyclooctadiene)chlororhodium (I) dimer (compound of formula II) and 0.12 mmol of azelaic acid were added in sequence to 30 mL of dichloromethane in a round-bottom flask, and stirred for 15 min; then 6 mmol of KPF6 (compound of formula III) pre-dissolved in 15 mL of water was added to the reaction solution, and stirring was continued for 45 min under nitrogen protection. The mixture was washed with water 3 times, the solvent was evaporated under reduced pressure, 80 mL of anhydrous ethanol was added, the mixture was allowed to stand at -5°C for 8 h, centrifuged, the supernatant was discarded, the light yellow precipitate was harvested, and dried to obtain a complex of formula IVa with a corresponding binaphthyl configuration. The elemental analysis results were consistent with the theoretical values, the product purity was 98.21%, and the recovery rate was 95.8%.

[0158] Example 17: Preparation of rare noble metal and chiral phosphine complex catalyst

[0159] The catalyst of rare noble metal and chiral phosphine complex was prepared by the method of reference example 1:

[0160] Under nitrogen protection, 3 mmol of R-(+)-1,1'-binaphthyl-2,2'-bisdiphenylphosphine (compound of formula I), 1 mmol of (1,5-cyclooctadiene)chlororhodium (I) dimer (compound of formula II) and 0.12 mmol of adipic acid were added to 30 mL of dichloromethane in a round-bottom flask in sequence, and stirred for 15 min; then 6 mmol of KPF6 (compound of formula III) pre-dissolved in 15 mL of water was added to the reaction solution, and stirring was continued for 45 min under nitrogen protection, washed with water 3 times, the solvent was evaporated under reduced pressure, 80 mL of anhydrous ethanol was added, and the mixture was allowed to stand at -5°C for 8 h, centrifuged, the supernatant was discarded, the light yellow precipitate was harvested, and dried to obtain a complex of formula IVa with a corresponding binaphthyl configuration. The elemental analysis results were consistent with the theoretical values, the product purity was 97.73%, and the recovery rate was 96.2%.

[0161] Example 18: Preparation of rare noble metal and chiral phosphine complex catalyst

[0162] The catalyst of rare noble metal and chiral phosphine complex was prepared by the method of reference example 1:

[0163] Under nitrogen protection, 3 mmol of S-(-)-1,1'-binaphthyl-2,2'-bisdiphenylphosphine (compound of formula I), 1 mmol of (1,5-cyclooctadiene)chlororhodium (I) dimer (compound of formula II) and 0.12 mmol of adipic acid were added to 30 mL of dichloromethane in a round-bottom flask in sequence, and stirred for 15 min; then 6 mmol of KPF6 (compound of formula III) pre-dissolved in 15 mL of water was added to the reaction solution, and stirring was continued for 45 min under nitrogen protection, washed with water 3 times, the solvent was evaporated under reduced pressure, 80 mL of anhydrous ethanol was added, and the mixture was allowed to stand at -5°C for 8 h, centrifuged, the supernatant was discarded, the light yellow precipitate was harvested, and dried to obtain a complex of formula IVa with a corresponding binaphthyl configuration. The elemental analysis results were consistent with the theoretical values, the product purity was 98.05%, and the recovery rate was 95.4%.

[0164] Example 19: Preparation of rare noble metal and chiral phosphine complex catalyst

[0165] Reference Example 1 method was used to prepare a catalyst of a rare noble metal and a chiral phosphine complex, wherein the caproic acid used was replaced by an equimolar amount of formic acid, acetic acid or propionic acid, and the recovery rates of the three batches of products calculated by precious metals were 73.3%, 79.6% and 84.4%, respectively. Reference Example 2 method was used to prepare a catalyst of a rare noble metal and a chiral phosphine complex, wherein the caproic acid used was replaced by an equimolar amount of formic acid, acetic acid or propionic acid, and the recovery rates of the three batches of products calculated by precious metals were 75.1%, 81.4% and 85.3%, respectively. The results of this example show that the recovery rate is significantly reduced when short-chain acids are used, and the shorter the chain, the lower the recovery rate.

[0166] Example 20: Preparation of rare noble metal and chiral phosphine complex catalyst

[0167] Reference Example 1 method for preparing a catalyst of a rare noble metal and a chiral phosphine complex, wherein the amount of hexanoic acid used is changed to 0, 0.05mmol, 0.1mmol, 0.3mmol or 0.6mmol, and the recovery rates of 5 batches of products calculated by precious metals are 51.4%, 81.6%, 92.7%, 95.7%, and 96.1%, respectively. Reference Example 2 method for preparing a catalyst of a rare noble metal and a chiral phosphine complex, wherein the amount of hexanoic acid used is changed to 0, 0.05mmol, 0.1mmol, 0.3mmol or 0.6mmol, and the recovery rates of 5 batches of products calculated by precious metals are 53.7%, 80.3%, 93.2%, 95.3%, and 96.4%, respectively. In further experiments, with reference to Examples 3 to 14, but when the amount of organic acid is changed to 0, the recovery rates are all less than 60%. In further experiments, with reference to Examples 3 to 14, but when the amount of organic acid is changed to 0.05mmol, the recovery rates are all less than 85%. In further experiments, referring to Examples 3 to 14, but when the amount of organic acid was changed to 0.1 mmol, the recovery rates were all within the range of 90% to 94%. In further experiments, referring to Examples 3 to 14, but when the amount of organic acid was changed to 0.6 mmol, the recovery rates were all within the range of 93% to 97%. The results of this embodiment show that the recovery rate is significantly reduced when the amount of organic acid is less than 0.1 mmol, and the organic acid has a good recovery rate when the amount is in the range of 0.1 to 0.6 mmol.

[0168] Example 21: Preparation of rare noble metal and chiral phosphine complex catalyst

[0169] Reference Examples 1 to 18 methods are used to prepare catalysts of rare precious metals and chiral phosphine complexes, wherein the KPF6 used is replaced by an equimolar amount of sodium hexafluorophosphate, and the obtained products have a recovery rate calculated as precious metals in the range of 93% to 96%, and the product purity is greater than 98%. Reference Examples 1 to 18 methods are used to prepare catalysts of rare precious metals and chiral phosphine complexes, wherein the KPF6 used is replaced by an equimolar amount of potassium tetrafluoroborate, and the obtained products have a recovery rate calculated as precious metals in the range of 93% to 96%, and the product purity is greater than 97%. Reference Examples 1 to 18 methods are used to prepare catalysts of rare precious metals and chiral phosphine complexes, wherein the KPF6 used is replaced by an equimolar amount of sodium tetrafluoroborate, and the obtained products have a recovery rate calculated as precious metals in the range of 94% to 96%, and the product purity is greater than 97%. The catalyst prepared using tetrafluoroborate has the chemical structural formula shown in the following formula IVb of the corresponding binaphthyl configuration (molecular formula C52H44F4P2BRh, molecular weight Mr=920.6):

[0170] .

[0171] Example 22: Preparation of rare noble metal and chiral phosphine complex catalyst

[0172] The catalyst of rare noble metal and chiral phosphine complex was prepared by the method of reference example 1:

[0173] Under nitrogen protection, 2.5 mmol of R-(+)-1,1'-binaphthyl-2,2'-bisdiphenylphosphine (compound of formula I), 1 mmol of (1,5-cyclooctadiene)chlororhodium (I) dimer (compound of formula II) and 0.15 mmol of hexanoic acid were added to 25 mL of dichloromethane in a round-bottom flask in sequence, and stirred for 10 min; then 5 mmol of KPF6 (compound of formula III) pre-dissolved in 20 mL of water was added to the reaction solution, and stirring was continued for 40 min under nitrogen protection, washed with water 3 times, the solvent was evaporated under reduced pressure, 80 mL of anhydrous ethanol was added, and the mixture was allowed to stand at -5°C for 8 h, centrifuged, the supernatant was discarded, the light yellow precipitate was harvested, and dried to obtain a complex of formula IV with a corresponding binaphthyl configuration. The elemental analysis results were consistent with the theoretical values, the product purity was 97.26%, and the recovery rate was 95.3%.

[0174] Example 23: Preparation of rare noble metal and chiral phosphine complex catalyst

[0175] The catalyst of rare noble metal and chiral phosphine complex was prepared by the method of reference example 1:

[0176] Under nitrogen protection, 4 mmol of R-(+)-1,1'-binaphthyl-2,2'-bisdiphenylphosphine (compound of formula I), 1 mmol of (1,5-cyclooctadiene)chlororhodium (I) dimer (compound of formula II) and 0.3 mmol of hexanoic acid were added in sequence to 45 mL of dichloromethane in a round-bottom flask, and stirred for 25 min; then 7 mmol of KPF6 (compound of formula III) pre-dissolved in 10 mL of water was added to the reaction solution, and stirring was continued for 60 min under nitrogen protection, washed with water 3 times, the solvent was evaporated under reduced pressure, 80 mL of anhydrous ethanol was added, and the mixture was allowed to stand at -5°C for 8 h, centrifuged, the supernatant was discarded, the light yellow precipitate was harvested, and dried to obtain a complex of formula IV with a corresponding binaphthyl configuration. The elemental analysis results were consistent with the theoretical values, the product purity was 97.76%, and the recovery rate was 95.8%.

[0177] In some supplementary experiments, the inventors referred to the methods of Examples 1, 3 and 6, but used equimolar amounts of the following compounds of Formula III: ammonium hexafluorophosphate, ammonium tetrafluoroborate, lithium hexafluorophosphate and lithium tetrafluoroborate. The purity of the obtained products was greater than 96% and the recovery rate was within the range of 95% to 97%, indicating that these fluoride-containing salts are also effective.

[0178] Test Example 2: Application of complex catalyst

[0179] The complex catalyst obtained in Example 1 and itaconic acid were dissolved in dichloromethane at a molar ratio of 1:140, and hydrogenation reaction was carried out in an autoclave. The enantiomeric selectivity of the final product obtained was 98.3%ee.

[0180] Test Example 3: Stability of Complex Catalyst

[0181] The catalysts obtained in Examples 1 to 18 and Examples 21 to 23 were placed open at room temperature for 12 months, and the purity of each catalyst was measured using the method of Test Example 1. The results were all within the range of 95% to 98%. For example, the purity of the catalyst in Example 23 after being placed at room temperature for 12 months was 96.93%, which was substantially unchanged from the initial purity. This indicates that the catalyst obtained in the present invention has excellent stability.

[0182] The present invention illustrates the detailed method of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed method, that is, it does not mean that the present invention must rely on the above-mentioned detailed method to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A method for preparing a complex as shown in the following formula IV: in, X is boron and n is 4 or X is phosphorus and n is 6; The method comprises the following steps: (i) under nitrogen protection, adding the compound of formula I, i.e. 1,1'-binaphthyl-2,2'-bisdiphenylphosphine, the compound of formula II, i.e. (1,5-cyclooctadiene)chlororhodium (I) dimer, and alkanoic acid to the organic solvent of dichloromethane in sequence, and stirring for 10 to 30 minutes to make them uniform; the amount of the organic solvent used is 20 to 50 mL per 1 mmol of the compound of formula II; the alkanoic acid is selected from hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, adipic acid, and azelaic acid; the molar ratio of the compound of formula I to the compound of formula II is 2.5 to 5:1, and the molar ratio of the alkanoic acid to the compound of formula II is 0.1 to 0.6:1; (ii) adding a compound of formula III represented by the chemical formula MXFn, i.e., a fluoride salt, to the mixture obtained in step (i), and continuing stirring under nitrogen protection to allow the reaction to proceed to completion; the compound of formula III represented by the chemical formula MXFn is KPF6 or potassium tetrafluoroborate, and M is K + , X is boron and n is 4 or X is phosphorus and n is 6, the compound of formula III is pre-dissolved in water; the molar ratio of the compound of formula III to the compound of formula II is 4 to 8:1; (iii) washing with water, distilling off the solvent under reduced pressure, adding anhydrous ethanol, leaving the mixture in a cold place to allow precipitation, and drying the collected precipitate to obtain a complex.

2. The method according to claim 1, wherein the complex has one of the following structures:

3. The method according to claim 1, wherein the compound of formula I is R-(+)-1,1'-binaphthyl-2,2'-bisdiphenylphosphine or S-(-)-1,1'-binaphthyl-2,2'-bisdiphenylphosphine.

4. The method according to claim 1, wherein in step (ii), 10 to 30 mL of water is used to dissolve every 6 mmol of the compound of formula III.

5. The method according to claim 1, wherein in step (ii), the material is stirred for 10 to 30 minutes under nitrogen protection.

6. The method according to claim 1, wherein in step (iii), washing with water is performed 2 to 4 times.

7. The method according to claim 1, wherein in step (iii), the amount of anhydrous ethanol added is 50-100 mL per 1 mmol of the compound of formula II.

8. The method according to claim 1, wherein in step (iii), the material is allowed to stand at -10 to 0°C for 6 to 12 hours.

9. The method according to claim 1, wherein in step (iii), the precipitate is collected by centrifugation and the supernatant is discarded.

10. The method according to claim 1, comprising the steps of: (i) under nitrogen protection, 3 mmol of the compound of formula I, i.e., 1,1'-binaphthyl-2,2'-bisdiphenylphosphine, 1 mmol of the compound of formula II, i.e., (1,5-cyclooctadiene)chlororhodium (I) dimer, and 0.2 mmol of alkanoic acid were added to 30 mL of dichloromethane in a round-bottom flask in sequence, and stirred for 15 min; (ii) adding 6 mmol of potassium hexafluorophosphate or potassium tetrafluoroborate of the compound of formula III pre-dissolved in 15 mL of water to the mixture obtained in step (i), and continuing stirring for 45 min under nitrogen protection; (iii) Wash with water three times, evaporate the solvent under reduced pressure, add 80 mL of anhydrous ethanol, incubate at -5 °C for 8 h, centrifuge, discard the supernatant, harvest the precipitate, and dry to obtain the complex.

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