An amphiphilic chiral phosphoric acid catalyst and a method for preparing the same

Abstract

The application discloses an amphiphilic chiral phosphoric acid catalyst, belongs to the technical field of organic compounds and asymmetric organic catalytic synthesis, and is a compound shown in the following formula (1): (1) wherein R is 2,4,6-(iPr)3-C6H3, 3,5-(Me)2-C6H3, 3,5-(F)2-C6H3, 4-(anthracen-9-yl) or 4-Naphthyl. The product has a hydrophobic skeleton and a hydrophilic ion pair at the same time, can be uniformly dissolved in nonpolar organic solvents, polar protic / aprotic solvents, pure water phases and water / oil two-phase systems, is suitable for the solvent environment of most organic synthesis reactions, and does not need to adjust the structure of the catalyst for different reactions.

Description

Technical Field

[0001] This invention belongs to the field of organic compound and asymmetric organic catalytic synthesis technology, specifically relating to an amphiphilic chiral phosphoric acid catalyst and its preparation method. Background Technology

[0002] Chiral phosphoric acid is an important class of Brønsted acid chiral catalysts, widely used in asymmetric C-C and CN bond construction reactions. Traditional BINOL / SPINOL-type chiral phosphoric acid generally has a strongly hydrophobic structure, is soluble only in organic solvents, and exhibits poor solubility, significantly reduced activity and selectivity in aqueous / green systems; it also suffers from drawbacks such as difficult recovery, high cost, and limited substrate applicability.

[0003] Therefore, how to design, synthesize, and screen novel and highly efficient chiral catalysts, and how to address the selectivity, applicability, and stability of chiral phosphoric acid catalysts are problems that urgently need to be overcome by those skilled in the art. Summary of the Invention

[0004] To address the aforementioned problems, this invention provides a method for preparing a permeable electrode with excellent electrocatalytic performance and significant magnetic responsiveness by doping it with iron(III) oxide as a key functional component. This method aims to simultaneously improve the electrode's oxygen evolution potential, conductivity, and stability, and to impart magnetism to it, thereby solving the problems of easy loss and difficult recovery of particulate / packing electrodes, and utilizing a magnetic field to enhance mass transfer and separation processes within the reactor.

[0005] To achieve the above objectives, this application provides an amphiphilic chiral phosphoric acid catalyst, which is a compound represented by the following formula (1): ; (1) Wherein: R is 2,4,6-(iPr)3-C6H3, 3,5-(Me)2-C6H3, 3,5-(F)2-C6H3, 4-(anthracen-9-yl) or 4-Naphthyl.

[0006] Furthermore, consider the compound represented by formula (2): ; (2).

[0007] A method for preparing an amphiphilic chiral phosphoric acid catalyst includes the following steps: (1) Compounds 1,1'-bi-2,2'-dimethoxybinaphthylene and 1,3-dibromo-5,5-dimethylhydantoin were added to a flask, dissolved in anhydrous dichloromethane, and reacted completely under an argon atmosphere. The reaction was then quenched with sodium sulfite aqueous solution, separated, and extracted and dried to obtain yellow solid compound B for later use. (2) The yellow solid compound B obtained in step (1) is added to a flask together with 1,3-diiodo-5,5-dimethylhydantoin and bismuth trifluoromethanesulfonate. After being dissolved in anhydrous dichloromethane, the reaction is allowed to proceed until it is complete. The reaction is then quenched by sodium sulfite aqueous solution, separated, and then extracted and dried to obtain yellow solid compound C for later use. (3) The yellow solid compound C obtained in step (2), 2-naphthoic acid, anhydrous potassium carbonate, tris(dibenzylacetone)palladium and triphenylphosphine are mixed together, and then anhydrous N,N-dimethylformamide is added. After replacing the argon gas three times, the system is sealed for reaction. After completion, the mixture is washed, filtered and dried to obtain a light yellow solid compound D for later use. (4) Add the pale yellow solid compound D obtained in step (3) to anhydrous dichloromethane, stir until completely dissolved, then add boron tribromide dichloromethane solution dropwise. After the reaction is completed, quench the reaction with ultrapure water and separate the liquid. Finally, extract and dry to obtain pale yellow solid compound E for later use. (5) The pale yellow solid compound E obtained in step (4), triphenylphosphine, tris(dibenzylacetone)dipalladium and anhydrous ethylene glycol were mixed, and the system was sealed after purging argon three times. After the reaction was completed, the system was filtered and chromatographically treated to obtain orange-yellow solid compound F for later use. (6) Add the orange-yellow solid compound F obtained in step (5) to anhydrous pyridine, stir under argon protection until completely dissolved, then slowly add phosphorus oxychloride dropwise. After the reaction is complete, add deionized water to complete the hydrolysis and cyclization of the phosphate ester, and finally extract and dry to obtain the finished product.

[0008] Further, in step (1), the amount of 1,1'-bi-2,2'-dimethoxybinaphthylene used is 1000 mg; the amount of 1,3-dibromo-5,5-dimethylhydantoin used is 1910 mg; the amount of anhydrous dichloromethane used is 40 mL; the mass fraction of the sodium sulfite aqueous solution is 5%; the separation and subsequent specific operations are as follows: after standing separation, the aqueous phase is extracted three times with dichloromethane, all organic phases are combined, dried with anhydrous magnesium sulfate and filtered, and the filtrate is concentrated to dryness using a vacuum rotary evaporator to obtain compound B.

[0009] Further, in step (2), the amount of compound B used is 1600 mg; the amount of 1,3-diiodo-5,5-dimethylhydantoin used is 2670 mg; the amount of bismuth trifluoromethanesulfonate used is 333 mg; the amount of anhydrous dichloromethane used is 40 mL; the mass fraction of the sodium sulfite aqueous solution is 5%; the separation and subsequent specific operations are as follows: after standing separation, the aqueous phase is extracted three times with dichloromethane, all organic phases are combined, dried with anhydrous magnesium sulfate and filtered, the filtrate is concentrated to dryness using a vacuum rotary evaporator to obtain the crude product, and then the crude product is separated and purified by 200-300 mesh silica gel column chromatography to obtain compound C.

[0010] Further, in step (3), the amount of compound C used is 100 mg; the amount of 2-naphthylboronic acid used is 47.4 mg; the amount of anhydrous potassium carbonate used is 76.1 mg; the amount of tris(dibenzylacetone)palladium used is 6.3 mg; the amount of triphenylphosphine used is 7.2 mg; the amount of anhydrous N,N-dimethylformamide used is 5 mL; the washing, filtration and subsequent specific operations are as follows: first, remove the anhydrous N,N-dimethylformamide solvent by vacuum distillation, add dichloromethane to the residue to dissolve it, wash twice with saturated ammonium chloride aqueous solution and twice with saturated sodium chloride aqueous solution, back-extract the aqueous phase once with dichloromethane, combine all organic phases, dry with anhydrous magnesium sulfate and filter, concentrate the filtrate to dryness under vacuum to obtain crude product, and purify the crude product by preparative thin-layer chromatography to obtain compound D.

[0011] Further, in step (4), the amount of compound D used is 250 mg; the amount of anhydrous dichloromethane used is 9 mL; the amount of boron tribromide dichloromethane solution used is 1.68 mL, and its concentration is 1 mol / L; the extraction, drying and subsequent specific operations are as follows: the aqueous phase is extracted three times with dichloromethane, all organic phases are combined, washed successively with saturated sodium bicarbonate aqueous solution and saturated sodium chloride aqueous solution, dried with anhydrous magnesium sulfate and filtered, the filtrate is concentrated under reduced pressure to dryness to obtain crude product, and the crude product is purified by silica gel column chromatography to obtain compound E.

[0012] Further, in step (5), the amount of compound E used is 50 mg; the amount of triphenylphosphine used is 55.0 mg; the amount of tris(dibenzylacetone)dipalladium used is 3.2 mg; the amount of anhydrous ethylene glycol used is 200 μL; the specific operation after the reaction is completed is to cool the system to room temperature, add dichloromethane to dilute the reaction solution, wash with deionized water and saturated sodium chloride aqueous solution in sequence, dry the organic phase with anhydrous magnesium sulfate and filter, concentrate the filtrate under reduced pressure to dryness to obtain crude product, and purify the crude product by silica gel column chromatography to obtain compound F.

[0013] Further, in step (6), the amount of compound F used is 100 mg; the amount of anhydrous pyridine used is 37.0 mL; the amount of phosphorus oxychloride used is 1 mL; the specific operation after the reaction is completed is to slowly add 50.0 mL of deionized water to the system, heat to reflux and stir for 3 h to complete the hydrolysis and cyclization of phosphate ester, cool to room temperature after completion, add dichloromethane to the system for extraction, wash the organic phase twice with saturated sodium bicarbonate aqueous solution and twice with 6 mol / L hydrochloric acid, separate the aqueous phase and back-extract with dichloromethane three times, combine all organic phases, dry with anhydrous sodium sulfate and filter, concentrate the filtrate under reduced pressure to dryness to obtain crude product, separate and purify the crude product by silica gel column chromatography, wash and purify again with 6 mol / L hydrochloric acid, extract with dichloromethane and concentrate under reduced pressure to obtain the finished product.

[0014] This invention modifies the classic chiral phosphate backbone: The two naphthalene rings of the naphthalene core are connected by 1,1'-C-bonds to form a fixed R-type or S-type axial chiral configuration. The two naphthalene rings are arranged in a non-coplanar dihedral angle, which constitutes the basic three-dimensional framework of the molecule. The 2,2'-cyclic phosphate group is located in the inner region of the naphthalene core, with two oxygen atoms attached to the 2-position of the two naphthalene rings, forming a six-membered closed ring structure together with the central phosphorus atom, which is located in the chiral pocket core region of the molecule. Two 2-naphthyl substituents at the 3,3'-positions are respectively attached to the 3-positions of the two naphthalene rings, symmetrically distributed on the left and right sides of the binaphthyl nucleus, extending outward to form a steric barrier, and together with the binaphthyl nucleus, they form a chiral catalytic pocket with a fixed opening size and stereoconfiguration. Two triphenyl quaternary phosphonium cationic groups at the 6,6'- positions are respectively attached to the 6-position of the two naphthalene rings and are symmetrically distributed on the upper and lower outer sides of the binaphthalene core, forming a spatially separated and site-matched arrangement with the inner cyclic phosphate active center. The two bromide anions form ion pairs with the two triphenyl quaternary phosphonium cations, respectively, and are distributed around the quaternary phosphonium cations, corresponding one-to-one with the cations to maintain the overall electroneutrality of the molecule.

[0015] The pre-constructed binaphthalene core of the chiral catalytic environment has a fixed-axis chiral configuration, which, combined with the rigid steric hindrance of the 3,3'-position 2-naphthyl group, forms a nanoscale chiral catalytic pocket with a fixed stereoconfiguration and a single chiral bias on the inside of the molecule. This pocket only allows the substrate to enter with a specific spatial orientation, providing an inherent basis for stereoselective control of the reaction and fundamentally avoiding the generation of non-target chiral products.

[0016] Synergistic substrate activation through dual active sites: When the reactant enters the reaction system, the two catalytic active sites of the product are simultaneously and synergistically activated. The Brønsted acid center of the cyclic phosphate within the chiral pocket forms hydrogen bonds with the electrophilic groups of the substrate (such as imino, carbonyl, epoxy, etc.) through hydroxyl groups, or achieves electrophilic activation of the substrate through proton transfer, significantly reducing the activation energy barrier of the reaction; The triphenyl quaternary phosphonium Lewis base center on the outer side of the molecule coordinates with the nucleophilic groups of the substrate (such as aldehydes, ketones, active methylene groups, enol silyl ethers, etc.) through the lone pair electrons of the phosphorus atom, generating a reaction intermediate with stronger nucleophilicity and realizing the nucleophilic activation of the substrate. The two active centers achieve spatial matching of activation sites through the precise spatial arrangement of the binaphthyl skeleton, which can simultaneously bind and activate both electrophilic and nucleophilic substrates, bringing the two reaction substrates closer to the optimal reaction distance, achieving synergistic catalysis and significantly improving the reaction rate.

[0017] Directed reactions and stereoselective product generation: Two substrates simultaneously activated by dual active centers can only undergo target reactions such as addition, cyclization, and coupling in a chiral catalytic pocket with a fixed configuration, in a direction that conforms to the chiral orientation, to directionally generate target products with a single chiral configuration, thus achieving the core objective of asymmetric catalysis.

[0018] After the product dissociation and catalyst recycling reaction are completed, the hydrogen bonds and coordination between the generated target product and the active center of the catalyst disappear, and the product naturally dissociates from the chiral catalytic pocket. The catalyst is restored to its initial structure and active state and can directly participate in the next round of catalytic reaction, thus achieving multiple cycles of use.

[0019] The aforementioned effects are directly derived from the technical solution of the 6-step site-selective synthesis process of this product. The synthetic route adopts a stepwise substitution strategy of "first brominating the 6,6' position, then iodizing the 3,3' position". Each step of the reaction only involves transformation at the target site, without side reactions of multiple substitution or misplacement. Each step has a mature purification method, which solves the problem of easy formation of isomers due to multiple substitution of the binaphthyl skeleton.

[0020] The present invention has the following advantages over the prior art: This invention features a unique structural design for an amphiphilic catalyst, enabling it to operate efficiently in aqueous and even solvent-free systems. This aligns perfectly with current trends in green chemistry and significantly reduces environmental impact. This effect stems directly from the product's amphiphilic structure: a hydrophobic rigid aromatic ring framework paired with a hydrophilic quaternary phosphonium salt ion pair. Traditional BINOL phosphoric acid catalysts can only be dissolved in nonpolar organic solvents such as toluene and dichloromethane. This product, however, possesses both a hydrophobic framework and hydrophilic ion pairs, allowing for uniform dissolution in nonpolar organic solvents, polar protic / aprotic solvents, pure aqueous phases, and water-oil two-phase systems. It is compatible with the solvent environments of most organic synthesis reactions, eliminating the need to adjust the catalyst structure for different reactions. Attached Figure Description

[0021] Figure 1 The above is the 1H NMR spectrum of the catalyst corresponding to Example 1 of this invention; Figure 2 The above is the 1H NMR spectrum of the catalyst corresponding to Example 2 of this invention; Figure 3 The above is the 1H NMR spectrum of the catalyst corresponding to Example 3 of this invention; Figure 4 This is the 1H NMR spectrum of the host-guest assembly corresponding to Example 3 of the present invention; Figure 5 This is the DOSY spectrum corresponding to Embodiment 3 of the present invention. Detailed Implementation

[0022] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions in the embodiments of this invention will be clearly and completely described below in conjunction with the embodiments of this invention. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of the embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0023] In the embodiments, it should be noted that any processes not specifically described below are those that can be implemented or understood by those skilled in the art by referring to existing technology. Reagents or instruments whose manufacturers are not specified are considered to be conventional products that can be purchased commercially.

[0024] Example 1: An amphiphilic chiral phosphoric acid catalyst, which is a compound represented by the following formula (1): ; (1) Wherein: R is 2,4,6-(iPr)3-C6H3; its 1H NMR spectrum is attached. Figure 1 As shown.

[0025] Example 2: An amphiphilic chiral phosphoric acid catalyst, which is a compound represented by the following formula (1): ; (1) Wherein: R is 4-(anthracen-9-yl); its 1H NMR spectrum is attached. Figure 2 As shown.

[0026] Example 3: An amphiphilic chiral phosphoric acid catalyst, prepared by the following method: (1) Weigh compound A (1,1'-bi-2,2'-dimethoxybinaphthyl, 1000 mg, 3.181 mmol) and 1,3-dibromo-5,5-dimethylhydantoin (DBH, 1910 mg, 6.678 mmol) into a 125 mL round-bottom flask, add 40 mL of anhydrous dichloromethane, and stir until the starting material is completely dissolved. Under an argon atmosphere, stir at room temperature for 24 h, during which the reaction is monitored by thin-layer chromatography (TLC) until the starting material compound A is completely converted. After the reaction is completed, add 5% sodium sulfite aqueous solution to the reaction system to quench the reaction, allow it to stand and separate the liquids, extract the aqueous phase three times with dichloromethane, combine all organic phases, dry them with anhydrous magnesium sulfate and filter, concentrate the filtrate to dryness using a vacuum rotary evaporator to obtain a yellow solid compound B (1600 mg, crude product) with yellow-green fluorescence.

[0027] (2) Weigh compound B (1600 mg, 3.390 mmol), 1,3-diiodo-5,5-dimethylhydantoin (DIH, 2670 mg, 6.780 mmol), and bismuth trifluoromethanesulfonate (Bi(OTf)3, 333 mg, 0.508 mmol, 15 mol%) into a 125 mL round-bottom flask, add 40 mL of anhydrous dichloromethane, and stir until the solid is completely dissolved. Stir the reaction at room temperature for 12 minutes. The reaction was monitored by TLC until the starting compound B was completely converted. After the reaction was complete, a 5% sodium sulfite aqueous solution was added to quench the reaction until no oxidizing property was detected by starch-KI test paper, at which point the reaction solution was a deep orange-yellow color. The mixture was allowed to stand and separated. The aqueous phase was extracted three times with dichloromethane. All organic phases were combined, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated to dryness using a vacuum rotary evaporator to obtain the crude product. The crude product was purified by silica gel column chromatography (200-300 mesh) to obtain a yellow solid compound C (636 mg).

[0028] (3) Under an argon protective atmosphere, compound C (100 mg, 0.1377 mmol), 2-naphthoic acid (47.4 mg, 0.2754 mmol, 2.0 equivalent), anhydrous potassium carbonate (76.1 mg, 0.5508 mmol, 4.0 equivalent), tris(dibenzylideneacetone)palladium (Pd2(dba)3, 6.3 mg, 0.0069 mmol, 5 mol%) and triphenylphosphine (PPh3, 7.2 mg, 0.0275 mmol, 20 mol%) were added sequentially to a dry Schlenk reaction tube. 5 mL of anhydrous N,N-dimethylformamide (DMF) was added, and the system was sealed after purging the argon gas three times. The reaction was stirred in an oil bath at 100 °C for 24 h. After the reaction was completed, the reaction system was cooled to room temperature, and the DMF solvent was removed by vacuum distillation. The residue was dissolved in dichloromethane, and washed twice with saturated ammonium chloride aqueous solution and twice with saturated sodium chloride aqueous solution. The aqueous phase was back-extracted once with dichloromethane. All organic phases were combined, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated to dryness under reduced pressure to obtain the crude product. The crude product was purified by preparative thin-layer chromatography (developing solvent: n-hexane / dichloromethane, volume ratio 3:2) to give a pale yellow solid compound D (63.5 mg).

[0029] (4) Under an argon atmosphere, compound D (250 mg, 0.3367 mmol) was added to a dry 100 mL two-necked flask, followed by 9 mL of anhydrous dichloromethane. The mixture was stirred until completely dissolved, and the system was cooled in an ice bath at 0 °C. A 1 mol / L boron tribromide (BBr3) dichloromethane solution (1.68 mL, 1.68 mmol, 5.0 equivalent) was slowly added dropwise to the system, keeping the system temperature below 5 °C during the addition. After the addition was complete, the ice bath was removed, and the mixture was allowed to return to room temperature and stirred for 24 h. The reaction was monitored by TLC until the starting material was completely converted. After the reaction was complete, the system was placed back in an ice bath, and excess boron tribromide was quenched by slowly adding ultrapure water. After quenching, the mixture was allowed to stand and separated. The aqueous phase was extracted three times with dichloromethane. All organic phases were combined and washed successively with saturated sodium bicarbonate aqueous solution and saturated sodium chloride aqueous solution. The mixture was dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated to dryness under reduced pressure to obtain the crude product. The crude product was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate, volume ratio 4:1) to give a pale yellow solid compound E (211 mg).

[0030] (5) Under an argon atmosphere, compound E (50 mg, 0.0700 mmol), triphenylphosphine (PPh3, 55.0 mg, 0.210 mmol, 3.0 equivalent), and tris(dibenzylacetone)palladium (Pd2(dba)3, 3.2 mg, 0.0035 mmol, 5 mol%) were added sequentially to a dry sealed tube. 200 μL of anhydrous ethylene glycol was added, and the tube was sealed after purging with argon three times. The tube was then placed in an oil bath at 150 °C and stirred for 2 h. After the reaction was complete, the system was cooled to room temperature, and the reaction solution was diluted with dichloromethane. The solution was washed sequentially with deionized water and saturated sodium chloride solution. The organic phase was dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated to dryness under reduced pressure to obtain the crude product. The crude product was purified by silica gel column chromatography (eluent: dichloromethane / methanol, v / v ratio 10:1) to obtain an orange-yellow solid compound F (48 mg).

[0031] (6) Compound F (100 mg, 4.590 mmol) was added to a dry 250 mL two-necked flask, along with 37.0 mL of anhydrous pyridine. The mixture was stirred under argon protection until completely dissolved. After cooling in an ice bath, phosphorus oxychloride (POCl3, 1 mL) was slowly added dropwise to the system. After the addition was complete, the mixture was brought back to room temperature and stirred for 8 h. The reaction was monitored by TLC until the starting material was completely converted. After the reaction was complete, 50.0 mL of deionized water was slowly added to the system, and the mixture was heated to reflux and stirred for 3 h to complete the hydrolysis and cyclization of the phosphate ester. After the reaction was complete, the mixture was cooled to room temperature, and dichloromethane was added to the system for extraction. The organic phase was washed twice with saturated sodium bicarbonate aqueous solution and twice with 6 mol / L hydrochloric acid. After separation, the aqueous phase was back-extracted three times with dichloromethane. All organic phases were combined, dried over anhydrous sodium sulfate, and filtered. The filtrate was concentrated to dryness under reduced pressure to obtain the crude product. The crude product was purified by silica gel column chromatography, followed by washing with 6 mol / L hydrochloric acid, extraction with dichloromethane, and concentration under reduced pressure to obtain the pure target product (84 mg). Its 1H NMR spectrum is attached. Figure 3 As shown.

[0032] Appendix Figure 4 This is due to the host-guest interaction between naphthalene and the host molecule. 1 1H NMR spectroscopy revealed the host-guest inclusion behavior of the guest molecule naphthalene in solution. The NMR of a mixture of guest naphthalene and amphiphilic chiral phosphoric acid showed a shift and broadening of the naphthalene NMR spectrum, demonstrating that the guest naphthalene can enter the cavity of the chiral phosphoric acid.

[0033] Appendix Figure 5 The obtained spectrum is a diffusely ordered nuclear magnetic resonance (DOSY) spectrum. The radius of the assembled structure can be calculated to be approximately 3.87 nm from the DOSY spectrum.

[0034] It should be noted that, in the description of this invention, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. Therefore, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of this invention, "a plurality of" means two or more, unless otherwise explicitly specified.

[0035] The above description is merely a preferred embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention are included within the scope of protection of the present invention.

Claims

1. An amphiphilic chiral phosphoric acid catalyst, characterized in that, The compound is shown in formula (1): ； （1） Wherein: R is 2,4,6-(iPr)3-C6H3, 3,5-(Me)2-C6H3, 3,5-(F)2-C6H3, 4-(anthracen-9-yl) or 4-Naphthyl.

2. The amphiphilic chiral phosphoric acid catalyst according to claim 1, characterized in that, The compound is shown in formula (2): ； （2）。 3. A method for preparing the amphiphilic chiral phosphoric acid catalyst as described in claim 2, characterized in that, Includes the following steps: (1) Take compound 1,1'-bi-2,2'-dimethoxybinaphthylene and 1,3-dibromo-5,5-dimethylhydantoin and add them together into a flask. Dissolve them in anhydrous dichloromethane and react them completely under an argon atmosphere. Then quench the reaction with sodium sulfite aqueous solution, separate the liquids, and then extract and dry to obtain yellow solid compound B for later use. (2) The yellow solid compound B obtained in step (1) is added to a flask together with 1,3-diiodo-5,5-dimethylhydantoin and bismuth trifluoromethanesulfonate. After being dissolved in anhydrous dichloromethane, the reaction is allowed to proceed until it is complete. The reaction is then quenched by sodium sulfite aqueous solution, separated, and then extracted and dried to obtain yellow solid compound C for later use. (3) The yellow solid compound C obtained in step (2), 2-naphthoic acid, anhydrous potassium carbonate, tris(dibenzylacetone)palladium and triphenylphosphine are mixed together, and then anhydrous N,N-dimethylformamide is added. After replacing the argon gas three times, the system is sealed for reaction. After completion, the mixture is washed, filtered and dried to obtain a light yellow solid compound D for later use. (4) Add the pale yellow solid compound D obtained in step (3) to anhydrous dichloromethane, stir until completely dissolved, then add boron tribromide dichloromethane solution dropwise. After the reaction is completed, quench the reaction with ultrapure water and separate the liquid. Finally, extract and dry to obtain pale yellow solid compound E for later use. (5) The pale yellow solid compound E obtained in step (4), triphenylphosphine, tris(dibenzylacetone)dipalladium and anhydrous ethylene glycol were mixed, and the system was sealed after purging argon three times. After the reaction was completed, the system was filtered and chromatographically treated to obtain orange-yellow solid compound F for later use. (6) Add the orange-yellow solid compound F obtained in step (5) to anhydrous pyridine, stir under argon protection until completely dissolved, then slowly add phosphorus oxychloride dropwise. After the reaction is complete, add deionized water to complete the hydrolysis and cyclization of the phosphate ester, and finally extract and dry to obtain the finished product.

4. The method for preparing an amphiphilic chiral phosphoric acid catalyst according to claim 3, characterized in that, In step (1), the amount of 1,1'-bi-2,2'-dimethoxybinaphthylene used was 1000 mg; the amount of 1,3-dibromo-5,5-dimethylhydantoin used was 1910 mg; the amount of anhydrous dichloromethane used was 40 mL; the mass fraction of the sodium sulfite aqueous solution was 5%; the separation and subsequent specific operations were as follows: after standing separation, the aqueous phase was extracted three times with dichloromethane, all organic phases were combined, dried with anhydrous magnesium sulfate and filtered, and the filtrate was concentrated to dryness using a vacuum rotary evaporator to obtain compound B.

5. The method for preparing an amphiphilic chiral phosphoric acid catalyst according to claim 3, characterized in that, In step (2), the amount of compound B used was 1600 mg; the amount of 1,3-diiodo-5,5-dimethylhydantoin used was 2670 mg; the amount of bismuth trifluoromethanesulfonate used was 333 mg; the amount of anhydrous dichloromethane used was 40 mL; the mass fraction of the sodium sulfite aqueous solution was 5%; the separation and subsequent specific operations were as follows: after standing separation, the aqueous phase was extracted three times with dichloromethane, all organic phases were combined, dried with anhydrous magnesium sulfate and filtered, the filtrate was concentrated to dryness using a vacuum rotary evaporator to obtain the crude product, and then the crude product was separated and purified by silica gel column chromatography with a mesh of 200-300 to obtain compound C.

6. The method for preparing an amphiphilic chiral phosphoric acid catalyst according to claim 3, characterized in that, The amount of compound C used in step (3) is 100 mg; the amount of 2-naphthoic acid is 47.4 mg; the amount of anhydrous potassium carbonate is 76.1 mg; the amount of tris(dibenzylacetone)palladium is 6.3 mg; the amount of triphenylphosphine is 7.2 mg; the amount of anhydrous N,N-dimethylformamide is 5 mL; the washing, filtration and subsequent specific operations are as follows: first, remove the anhydrous N,N-dimethylformamide solvent by vacuum distillation, add dichloromethane to the residue to dissolve it, wash twice with saturated ammonium chloride aqueous solution and twice with saturated sodium chloride aqueous solution, back-extract the aqueous phase once with dichloromethane, combine all organic phases, dry with anhydrous magnesium sulfate and filter, concentrate the filtrate to dryness under vacuum to obtain crude product, and purify the crude product by preparative thin-layer chromatography to obtain compound D.

7. The method for preparing an amphiphilic chiral phosphoric acid catalyst according to claim 3, characterized in that, The amount of compound D used in step (4) is 250 mg; the amount of anhydrous dichloromethane is 9 mL; the amount of boron tribromide dichloromethane solution is 1.68 mL with a concentration of 1 mol / L; the extraction, drying and subsequent specific operations are as follows: the aqueous phase is extracted three times with dichloromethane, all organic phases are combined, washed successively with saturated sodium bicarbonate aqueous solution and saturated sodium chloride aqueous solution, dried with anhydrous magnesium sulfate and filtered, the filtrate is concentrated to dryness under reduced pressure to obtain crude product, and the crude product is purified by silica gel column chromatography to obtain compound E.

8. The method for preparing an amphiphilic chiral phosphoric acid catalyst according to claim 3, characterized in that, The amount of compound E used in step (5) is 50 mg; the amount of triphenylphosphine is 55.0 mg; the amount of tris(dibenzylacetone)dipalladium is 3.2 mg; the amount of anhydrous ethylene glycol is 200 μL; the specific operation after the reaction is completed is to cool the system to room temperature, add dichloromethane to dilute the reaction solution, wash with deionized water and saturated sodium chloride aqueous solution in sequence, dry the organic phase with anhydrous magnesium sulfate and filter, concentrate the filtrate under reduced pressure to dryness to obtain crude product, and purify the crude product by silica gel column chromatography to obtain compound F.

9. The method for preparing an amphiphilic chiral phosphoric acid catalyst according to claim 3, characterized in that, The amount of compound F used in step (6) is 100 mg; the amount of anhydrous pyridine is 37.0 mL; the amount of phosphorus oxychloride is 1 mL; the specific operation after the reaction is completed is to slowly add 50.0 mL of deionized water to the system, heat to reflux and stir for 3 h to complete the hydrolysis and cyclization of phosphate ester, cool to room temperature after completion, add dichloromethane to the system for extraction, wash the organic phase twice with saturated sodium bicarbonate aqueous solution and twice with 6 mol / L hydrochloric acid, separate the aqueous phase and back-extract with dichloromethane three times, combine all organic phases, dry with anhydrous sodium sulfate and filter, concentrate the filtrate under reduced pressure to dryness to obtain crude product, separate and purify the crude product by silica gel column chromatography, wash and purify again with 6 mol / L hydrochloric acid, extract with dichloromethane and concentrate under reduced pressure to obtain the finished product.

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