Super-crosslinking photosensitive material and preparation method and application thereof

Abstract

The invention relates to a super-crosslinking photosensitive material as well as a preparation method and application thereof. According to the photosensitive material, photosensitive molecules such as 2, 4, 5, 6-tetra (9-carbazolyl)-isophthalonitrile, 1, 3-dicyano-2, 4, 5, 6-tetra (diphenylamino)-benzene, anthraquinone, thioxanthone and the like are used as a basic structural unit as a skeleton; according to the preparation method, p-xylylene dichloride, 1, 4-di (bromomethyl) benzene, 1, 3, 5-tri (bromomethyl) benzene or biphenyl xylylene dichloride is used as a cross-linking agent, and photosensitive molecules are bonded with the cross-linking agent to obtain the super-crosslinked photosensitive material with the photosensitive property. The photosensitive material is applied to the asymmetric alpha-hydroxylation reaction of beta-keto ester, and an asymmetric alpha-hydroxylation reaction process with oxygen as an oxidizing agent is developed. The method provided by the invention is environment-friendly and has relatively high stereoselectivity.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of photosensitive material preparation, and particularly relates to a super-crosslinked photosensitive material and a preparation method thereof, and the photosensitive material is applied to catalyze asymmetric alpha-hydroxylation of beta-keto ester. BACKGROUND

[0002] Beta-keto ester alpha-hydroxylation is a kind of structural unit with important biological activity, which is widely present in natural active substances, drug molecules, agricultural chemicals and fine chemicals. Traditional photocatalytic asymmetric alpha-hydroxylation of beta-keto ester mostly uses peroxide (such as organic peroxide or H2O2) as an oxidant (The Journal of Organic Chemistry, 2004, 69(23): 8165-8167.)(Synlett, 2009, 2009(16): 2659-2662.). However, these methods have certain limitations in green sustainability, substrate adaptability and chirality control. In recent years, the photocatalytic pathway using molecular oxygen as an oxidant as a green and sustainable technology provides a new solution for the asymmetric alpha-hydroxylation of beta-keto ester (Organic & Biomolecular Chemistry, 2021, 19(30): 6588-6592.). The photosensitive molecule absorbs photons and efficiently converts light energy into chemical energy to generate active oxygen species (such as singlet oxygen), thereby realizing the hydroxylation of the substrate. Unlike traditional oxidants, the molecular oxygen system has the remarkable characteristics of inexpensive and green oxidant, mild reaction conditions and high oxidation efficiency. However, the photosensitive molecules currently used in the alpha-hydroxylation reaction of beta-keto ester are all small organic molecules, which cannot be conveniently recycled and used, therefore, a series of photosensitive molecular materials that can be conveniently recycled are developed to solve the problem of non-recyclable use. SUMMARY

[0003] The present application aims to solve the problems of difficult separation and difficult recycling of traditional photosensitive molecules, and provides a super-crosslinked photosensitive material, a preparation method and application thereof. The photosensitive material takes 2, 4, 5, 6-tetrakis (9-carbazolyl)-m-dinitrile, 1, 3-dicyano-2, 4, 5, 6-tetrakis (diphenylamino)-benzene, anthraquinone and thioxanthone and other photosensitive molecules as the basic structural unit of the skeleton; in the preparation method, p-dichlorobenzyl, 1, 4-bis (bromomethyl) benzene, 1, 3, 5-tris (bromomethyl) benzene, biphenyl dichlorobenzyl and are used as crosslinking agents, the photosensitive molecules are linked with the crosslinking agents to obtain a super-crosslinked photosensitive material with photosensitive properties; the photosensitive material is applied to the asymmetric alpha-hydroxylation reaction of beta-keto ester, and an asymmetric alpha-hydroxylation reaction process using oxygen as an oxidant is developed. The present application is environmentally friendly and has high stereoselectivity.

[0004] To achieve the above object, the present application adopts the following technical solutions: An ultracrosslinking photosensitive material, the structural formula of which is as follows: ; Wherein, R 1 is a 4DPAIPN, 4CzIPN, anthraquinone or thioxanthone structural unit; R 2 is a 1,4-p-dimethylbenzene, 1,3,5-trimethylbenzene or 1,4-p-dimethylbenzene structural unit. The solid line represents a carbon-carbon bond, R 2 connected structural units can be other R 1 or R 2 ， But R 1 can only be connected with R 2 , and this structure is repeated to form an ultracrosslinking material finally; The preparation method of the ultracrosslinking photosensitive material comprises the following steps: Step one, adding photosensitive molecules, crosslinking agents and Lewis acids into a first solvent, then reacting at 60-100 ℃ for 18-26 h in an inert atmosphere; the reaction liquid is subjected to suction filtration, the solid crude product is washed first, then subjected to Soxhlet washing for 10-24 h to obtain an ultracrosslinking photosensitive material crude product; Wherein, the molar ratio of photosensitive molecules to crosslinking agents is 1:1-8; the molar ratio of Lewis acids to photosensitive molecules is 1-5:1; 0.3mmol~1.2mmol photosensitive molecules are added per 30 mL of the first solvent; The photosensitive molecules are thioxanthone, anthraquinone, 4CzIPN or 4DPAIPN; The crosslinking agents are p-dichlorobenzyl, 1, 4-di(bromomethyl)benzene, 1, 3, 5-tri(bromomethyl)benzene, biphenyl dichlorobenzyl; the Lewis acids are anhydrous ferric chloride or anhydrous aluminum chloride; The first solvent is 1,2-dichloroethane or dichloromethane; The mixed solvent is dichloromethane and methanol, and the volume ratio of the two is 1:1; The inert gas is argon or nitrogen.

[0005] Step two, drying the ultracrosslinking photosensitive material crude product obtained in the above step at 60-100 ℃ for 10-24 h to obtain an ultracrosslinking photosensitive material.

[0006] The washing in step one is washing with 0.5-2 mol of hydrochloric acid, water, methanol and dichloromethane respectively; the Soxhlet washing is carried out with 0.5-2 mol of hydrochloric acid, water and mixed solvent respectively; The application of the super-crosslinking photosensitive material is used for preparing optical purity high alpha-hydroxylate in the catalytic asymmetric alpha-hydroxylation reaction of beta-keto acid ester.

[0007] The method comprises the following steps: Step one, sequentially adding chiral ligand, metal catalyst and second solvent into a high-pressure sealed tube, then replacing and filling argon or nitrogen, stirring and reacting at 20-50 DEG C for 0.5-2 hours to obtain a complex; Step two, then sequentially adding beta-keto acid ester and super-crosslinking photosensitive material, replacing and filling 1-3 atmospheres of oxygen, stirring and reacting at-30 DEG C-30 DEG C under visible light for 2-30 hours to obtain alpha-hydroxylate of beta-keto acid ester; Wherein, 7-10 mg of chiral ligand, 3-7 mg of metal catalyst, 20-35 mg of beta-keto acid ester and 6-9 mg of super-crosslinking photosensitive material are added into every 2 mL of second solvent; The second solvent in step one is toluene, dimethylbenzene, dichloromethane, methanol, acetonitrile, tetrahydrofuran or methyl tert-butyl ether, preferably toluene; The chiral ligand in step one is a salen ligand, preferably ligand L; The structure of ligand L is as follows:

[0008] The metal catalyst in step one is Cu(OTf)2, Ni(OTf)2, Zn(OTf)2, Fe(OTf)2, Zr(acac)2 or Cu(OAc)2; The beta-keto acid ester in step two is 1-indanone-2-carboxylic acid (2-adamantane) ester, 1-indanone-2-carboxylic acid (methyl) ester or 1-indanone-2-carboxylic acid (1-adamantane) ester with different substituents such as methyl, methoxy, fluorine atom, chlorine atom and bromine atom; The super-crosslinking photosensitive material in step two is one of 4CzIPN-HCPs1, 4DPAIPN-HCPs1, AQ-HCPs1 and TX-HCPs1-TX-HCPs4.

[0009] The substantial features of the present application are: Currently, the photosensitive molecules used in the asymmetric alpha-hydroxylation reaction of beta-keto acid ester are mostly small-molecule photosensitive monomers, which are difficult to recover; the present application uses molecular oxygen instead of traditional oxidants, and connects small-molecule photosensitizers through a crosslinking agent to obtain a super-crosslinking photosensitive material with a photocatalytic center, so that the photosensitive catalyst can be recycled by simple filtration, and the catalytic activity is not obviously reduced.

[0010] The present application has the following beneficial effects: The application first proposes and synthesizes a super-crosslinking photosensitive material, and applies the photosensitive material to an asymmetric alpha-hydroxylation reaction of beta-keto acid ester, replaces existing small-molecule organic photosensitizers, realizes recycling and reuse of photocatalysts through simple filtration, and uses green and cheap oxygen instead of traditional peroxides, hypochlorite, high-valence iodine reagents and the like as an oxidizing agent for epoxidation reaction, thereby avoiding pollution and reducing reaction cost, and the yield of the target product is as high as 96%, and the enantiomeric excess value is as high as 92%. BRIEF DESCRIPTION OF DRAWINGS

[0011] Figure 1 is a Fourier infrared spectrum obtained in Example 1; Figure 2 is a Fourier infrared spectrum obtained in Example 2; Figure 3 is a Fourier infrared spectrum obtained in Example 3; Figure 4 is a Fourier infrared spectrum obtained in Example 4; Figure 5 is a Fourier infrared spectrum obtained in Example 5; Figure 6 is a Fourier infrared spectrum obtained in Example 6; Figure 7 is a Fourier infrared spectrum obtained in Example 7; Figure 8 is a solid-state carbon nuclear magnetic resonance spectrum obtained in Example 7; Figure 9 is a scanning electron microscope image obtained in Example 7; Figure 10 is a solid-state ultraviolet-visible diffuse reflectance spectrum obtained in Example 7; DETAILED DESCRIPTION

[0012] The technical solutions in the application will be described below in conjunction with specific embodiments, and it should be understood that the described embodiments are only some of the embodiments of the application, not all the embodiments. Based on the embodiments in the application, other embodiments obtained by those of ordinary skill in the art without creative labor are within the scope of protection of the application.

[0013] The chiral ligand L involved in the application is a known substance, and the ligand L is obtained according to the literature method (Advanced Synthesis & Catalysis, 2019, 361(7): 1673-1677.); the structural formula is as follows:

[0014] Example 1: Synthesis of hypercrosslinked photosensitive material 4CzIPN-HCPs1 prepared from photosensitive molecule 2, 4, 5, 6-tetra (9-carbazolyl) -1, 3-dicyanobenzene (4CzIPN)

[0015] Step one, 0.2433 g (1.5 mmol) of anhydrous ferric chloride, 0.42 g (2.4 mmol) of p-dichlorobenzene and 30 mL of 1, 2-dichloroethane were added to a 100 mL round-bottom flask, then 0.2364 g (0.3 mmol) of 4CzIPN was added to the flask, and the reaction was placed in an 80 ℃ oil bath and stirred for 24 h under an argon atmosphere.

[0016] Step two, after the reaction was completed, the reaction solution was suction filtered, and the solid product obtained by suction filtration was first washed with 2M hydrochloric acid, water, methanol and dichloromethane respectively.

[0017] Step three, then 2M hydrochloric acid, water and dichloromethane: methanol = 1:1 mixed solvent were used for Soxhlet washing respectively for 12 h, and the product obtained after Soxhlet washing was dried in a vacuum oven at 60 ℃ for 12 h to obtain the hypercrosslinked photosensitive material 4CzIPN-HCPs1.

[0018] By Figure 1 From the Fourier infrared spectrum of 4CzIPN-HCPs1, it can be seen that the characteristic absorption peaks at 2930 cm -1 and 2860cm -1 belong to the methylene stretching vibration peak in the structure of TX-HCPs4, which indicates that the synthesized photosensitive material is successfully connected by methylene. The characteristic peak at 2250 cm -1 in the figure corresponds to the stretching vibration peak of C-N in the material, which indicates that the 4CzIPN monomer is successfully polymerized into the material.

[0019] Example 2: Synthesis of hypercrosslinked photosensitive material 4DPAIPN-HCPs1 prepared from photosensitive molecule 1, 3-dicyano-2, 4, 5, 6-tetra (diphenyl amino) -benzene (4DPAIPN)

[0020] Step one, 0.2433 g (1.5 mmol) of anhydrous ferric chloride, 0.42 g (2.4 mmol) of p-dichlorobenzene and 30 mL of 1, 2-dichloroethane were added to a 100 mL round-bottom flask, then 0.2364 g (0.3 mmol) of 4CzIPN was added to the flask, and the reaction was placed in an 80 ℃ oil bath and stirred for 24 h under an argon atmosphere.

[0021] Step two, after the reaction, the reaction liquid was filtered, the solid product obtained by filtration was first washed with 2M hydrochloric acid, water, methanol, dichloromethane, Step three, then 2M hydrochloric acid, water, dichloromethane: methanol = 1:1 mixed solvent was used respectively for 12 h, and the product was dried in a vacuum oven at 60 ℃ for 12 h after the end of the extraction, to obtain the super cross-linked photosensitive material 4DPAIPN-HCPs1.

[0022] By Figure 2 Observing the Fourier infrared spectrum of 4DPAIPN-HCPs1, it can be seen that the characteristic absorption peaks at 2930 cm -1 and 2860 cm -1 belong to the methylene stretching vibration peak in the structure of TX-HCPs4, which shows that the synthesized photosensitive material is successfully connected by methylene. The characteristic peak at 2250 cm -1 in the figure corresponds to the stretching vibration peak of C-N in the material, which shows that the 4DPAIPN monomer is successfully polymerized into the material.

[0023] Example 3: Synthesis of super cross-linked photosensitive material AQ-HCPs1 prepared from photosensitive molecule anthraquinone (AQ):

[0024] Step one, 0.2433 g (1.5 mmol) of anhydrous ferric chloride, 0.42 g (2.4 mmol) of p-dichlorobenzene and 30 mL of 1,2-dichloroethane were added to a 100 mL round-bottom flask, then 0.2496 g (1.2 mmol) of AQ was added to the bottle, and the reaction was placed in an oil bath at 80 ℃, and stirred for 24 h under argon atmosphere.

[0025] Step two, after the reaction, the reaction liquid was filtered, the solid product obtained by filtration was first washed with 2M hydrochloric acid, water, methanol, dichloromethane.

[0026] Step three, then 2M hydrochloric acid, water, dichloromethane: methanol = 1:1 mixed solvent was used respectively for 12 h, and the product was dried in a vacuum oven at 60 ℃ for 12 h after the end of the extraction, to obtain the super cross-linked photosensitive material AQ-HCPs1.

[0027] By Figure 3 Observing the Fourier infrared spectrum of AQ-HCPs1, it can be seen that the characteristic absorption peaks at 2930 cm -1 and 2860 cm -1The characteristic absorption peak at this location is attributed to the methylene stretching vibration peak in the TX-HCPs4 structure, indicating that the synthesized photosensitive material is successfully linked through methylene groups.

[0028] Example 4: Synthesis of the hypercrosslinked photosensitizer TX-HCPs1 prepared from the photosensitizer molecule thioxanthone (TX):

[0029] Step 1: Add 0.2433 g (1.5 mmol) anhydrous ferric chloride, 0.42 g (2.4 mmol) p-dichlorobenzyl, and 30 mL of 1,2-dichloroethane to a 100 mL round-bottom flask. Then add 0.2544 g (1.2 mmol) TX to the flask. Place the reaction in an oil pan at 80 °C and stir for 24 h under an argon atmosphere.

[0030] Step 2: After the reaction is complete, the reaction solution is filtered. The solid product obtained by filtration is first washed with 2M hydrochloric acid, water, methanol, and dichloromethane respectively.

[0031] Step 3: Then, the product was extracted and washed with 2M hydrochloric acid, water, and a mixed solvent of dichloromethane and methanol (1:1) for 12 h. After extraction, the product was dried in a vacuum oven at 60 °C for 12 h to obtain the hypercrosslinked photosensitive material TX-HCPs1.

[0032] pass Figure 4 Observing the Fourier transform infrared spectrum of TX-HCPs1, we can see that 2930 cm⁻¹... -1 and 2860 cm -1 The characteristic absorption peak at 1705 cm⁻¹ is attributed to the methylene stretching vibration peak in the TX-HCPs4 structure, indicating that the synthesized photosensitive material is successfully linked via methylene groups. Furthermore, the peak at 1705 cm⁻¹ in the figure... -1 The characteristic peak appearing at the point corresponds to the stretching vibration peak of the carbonyl group in the material, indicating that the thioxanthone monomer was successfully polymerized into TX-HCPs4. Example 5: Synthesis of the hypercrosslinked photosensitizer TX–HCPs2, prepared from the photosensitizer molecule thioxanthone (TX) and 1,4-bis(bromomethyl)benzene:

[0033] Step one, 0.2433 g (1.5 mmol) of anhydrous ferric chloride, 0.5279 g (2 mmol) of 1, 4-bis (bromomethyl) benzene and 30 mL of 1, 2-dichloroethane were added to a 100 mL round-bottom flask, then 0.2544 g (1.2 mmol) of TX was added to the bottle, and the reaction was placed in an 80 ℃ oil bath and stirred for 24 h under an argon atmosphere.

[0034] Step two, after the reaction was completed, the reaction solution was suction filtered, and the solid product obtained by suction filtration was first washed with 2M hydrochloric acid, water, methanol and dichloromethane respectively.

[0035] Step three, then 2M hydrochloric acid, water and dichloromethane: methanol = 1:1 mixed solvent were used for Soxhlet washing respectively for 12 h, and the obtained product was dried in a vacuum oven at 60 ℃ for 12 h after Soxhlet extraction, to obtain the hypercrosslinked photosensitive material TX-HCPs2.

[0036] By Figure 5 From the Fourier infrared spectrum of TX-HCPs2, it can be seen that the characteristic absorption peaks at 2930 cm -1 and 2860 cm -1 belong to the methylene stretching vibration peak in the structure of TX-HCPs4, which shows that the synthesized photosensitive material is successfully connected by methylene. In addition, the characteristic peak at 1705 cm -1 in the figure corresponds to the stretching vibration peak of the carbonyl group in the material, which shows that the thioxanthone monomer is successfully polymerized into TX-HCPs4.

[0037] Example 6: Synthesis of hypercrosslinked photosensitive material TX-HCPs3 prepared from photosensitive molecule thioxanthone (TX) and 1, 3, 5-tris (bromomethyl) benzene:

[0038] Step one, 0.2433 g (1.5 mmol) of anhydrous ferric chloride, 0.5279 g (2 mmol) of 1, 4-bis (bromomethyl) benzene and 30 mL of 1, 2-dichloroethane were added to a 100 mL round-bottom flask, then 0.2544 g (1.2 mmol) of TX was added to the bottle, and the reaction was placed in an 80 ℃ oil bath and stirred for 24 h under an argon atmosphere.

[0039] Step two, after the reaction was completed, the reaction solution was suction filtered, and the solid product obtained by suction filtration was first washed with 2M hydrochloric acid, water, methanol and dichloromethane respectively.

[0040] Step three, then use 2M hydrochloric acid, water, dichloromethane: methanol = 1:1 mixed solvent respectively for 12 h, after the end of the extraction of the product obtained in the vacuum oven at 60 ℃ drying 12 h, get super cross-linked photosensitive material TX-HCPs3.

[0041] By Figure 6 Observation of Fourier infrared spectrum of TX-HCPs3, can see 2930 cm -1 and 2860 cm -1 The characteristic absorption peak in the structure of TX-HCPs4 belongs to methylene stretching vibration peak, which shows that the synthesized photosensitive material is successfully connected by methylene. In addition, the characteristic peak of 1705 cm -1 in the figure corresponds to the stretching vibration peak of carbonyl in the material, which shows that thioxanthone monomer is successfully polymerized into TX-HCPs4.

[0042] Example 7: Synthesis of super cross-linked photosensitive material TX-HCPs4 prepared by photosensitive molecule thioxanthone (TX) and biphenyl dichlorobenzene:

[0043] Step one, 0.2433 g (1.5 mmol) of anhydrous ferric chloride, 0.5023 g (2 mmol) of biphenyl dichlorobenzene and 30 mL of 1,2-dichloroethane were added to a 100 mL round-bottom flask, then 0.2544 g (1.2 mmol) of TX was added to the bottle, and the reaction was placed in an oil bath at 80 ℃, and stirred for 24 h under argon atmosphere.

[0044] Step two, after the reaction, the reaction liquid was filtered, and the solid product obtained by filtration was first washed with 2M hydrochloric acid, water, methanol and dichloromethane respectively.

[0045] Step three, then use 2M hydrochloric acid, water, dichloromethane: methanol = 1:1 mixed solvent respectively for 12 h, after the end of the extraction of the product obtained in the vacuum oven at 60 ℃ drying 12 h, get super cross-linked photosensitive material TX-HCPs4.

[0046] By Figure 7 Observation of Fourier infrared spectrum of TX-HCPs4, can see 2930 cm -1 and 2860 cm -1 The characteristic absorption peak in the structure of TX-HCPs4 belongs to methylene stretching vibration peak, which shows that the synthesized photosensitive material is successfully connected by methylene. In addition, the characteristic peak of 1705 cm -1The characteristic peak appearing at the point corresponds to the stretching vibration peak of the carbonyl group in the material, indicating that the thioxanthone monomer was successfully polymerized into TX-HCPs4.

[0047] pass Figure 8 13 ¹³C NMR confirmed the bonding mode of TX-HCPs4. In TX-HCPs4... 13 In the C10 NMR spectrum, the peak signal at 40 ppm is attributed to the carbon atom of the -CH2 group in TX-HCPs4, further confirming the connection between the thioxanthone monomer and the crosslinking agent molecule via a methylene group. The broad peak signal between 110 and 150 ppm is attributed to the carbon atom in the aromatic ring, i.e., the aromatic ring region of thioxanthone and the crosslinking agent. Furthermore, the peak signal at 220 ppm is attributed to the carbon atom of the C=O bond, indicating the successful introduction of the thioxanthone molecule.

[0048] pass Figure 9 Scanning electron microscopy was used to characterize the surface microstructure of the two functional materials. It can be seen that TX-HCPs4 has a rich pore structure, uniform and dense particle distribution and high surface roughness. These features not only increase the specific surface area of ​​the material, but also provide more active sites for the photocatalyst, resulting in higher photocatalytic efficiency.

[0049] pass Figure 10 The solid-state UV-Vis diffuse reflectance spectrum of the material shows that polymerization significantly alters its light absorption characteristics. In the figure, compared to the thioxanthone monomer, the absorption sideband of TX-HCPs4 exhibits a significant red shift, indicating that the polymerization process effectively expands the material's absorption range, enabling it to adapt to more complex lighting conditions.

[0050] Example 8:

[0051] Into a dry 15 mL high pressure tube equipped with a magnetic stir bar, 0.0071 g (0.011 mmol) of chiral ligand L, 0.0036 g (0.01 mmol) of Cu(OTf)2, 2 mL of dry toluene were added, the tube was flushed with argon and the complexation was carried out at 50 °C for 30 min with stirring. After the complexation, the reaction was cooled to -15 °C and 0.031 g (0.1 mmol) of 2-adamantyl 1-indanone-2-carboxylate (3a) and 25 wt% of hypercrosslinked photosensitive material based on the template substrate 3a (i.e. 7 materials obtained in Examples 1-7 were added, respectively) were added. The tube was then evacuated and flushed with 0.3 MPa of O2 and placed in a cold trap at -15 °C and stirred under white xenon lamp irradiation for 13 h. The progress of the reaction was monitored by TLC and after the reaction was completed, the reaction was vacuumed and dried. The residue was purified by column chromatography to give the corresponding product 4a. The enantioselectivity was determined by HPLC.

[0052] wherein the structures of the template substrate 3a and its corresponding product 4a in the steps are shown in the reaction scheme: The hypercrosslinked photosensitive materials described in Examples 1-7 were used according to the procedure described in Example 8 and the data obtained are shown in the following table:

[0053] Application Example 1:

[0054] Into a dry 15 mL high pressure tube equipped with a magnetic stir bar, 7.1 mg of chiral ligand, 3.49 mg of Cu(OTf)2, 2 mL of dry toluene were added, the tube was flushed with argon and the complexation was carried out at 50 °C for 30 min with stirring. After the complexation, 30.93 mg of 3a and 7.73 mg of TX-HCPs 4 were added. The reaction was placed in a cold trap at -15 °C and stirred under white xenon lamp irradiation for 13 h. After the reaction was completed, the reaction was purified by silica gel column chromatography with eluent of ethyl acetate: petroleum ether = 1:20 to give the hydroxylated product 4a with a yield of 93% and an ee value of 85%.

[0055]

[0056] The NMR, HRMS and HPLC data of the product obtained are as follows: 2-Adamantyl 2-hydroxy-1-indanone-2-carboxylate (4a) white solid; m.p. = 83-84 °C; 30.5 mg; 93.5%; 1H NMR (600 MHz, Chloroform-d) δ 7.80 (d, J = 7.6 Hz, 1H), 7.65 (t, J = 7.5 Hz, 1H), 7.50 (d, J = 7.7 Hz, 1H), 7.42 (t, J = 7.5 Hz, 1H), 4.95 (t, J = 3.5 Hz, 1H), 4.05 (s, 1H), 3.70 (d, J = 16.9 Hz, 1H), 3.29 (d, J = 16.9 Hz, 1H), 1.91 (s, 1H), 1.84 (s, 1H), 1.79–1.72 (m, 3H), 1.67 (d, J = 5.1 Hz, 2H), 1.61 (s, 2H), 1.56 (t, J = 3.3 Hz, 1H), 1.44–1.28 (m, 4H). HRMS (ESI) calcd for C 20 H 22 O4 ([M+Na] + ) = 349.1411, found: 349.1401.HPLC conditions: Chiralcel AD-H column (250 × 4.6 mm), hexane / i-PrOH = 80 / 20, 1 mL / min, 254 nm, τR(major) = 10.17 min, τR(minor) = 12.47 min. Example 2:

[0057] Into a dry 15 mL high pressure sealed tube, 7.1 mg chiral ligand, 3.49 mg Cu(OTf)2, 2 mL anhydrous toluene were added, the gas in the tube was replaced by argon, then the complexation was carried out at 50 °C for 30 min, after the complexation, 33.93 mg 3b and 8.48 mg TX-HCPs4 were added, and the reaction was placed in a -15 °C cold trap for 13 h, after the reaction was completed, the reaction solution was chromatographed using a silica gel column, eluent was ethyl acetate: petroleum ether = 1:20, and the hydroxylated product 4b was separated, with a yield of 81% and an ee value of 54%.

[0058]

[0059] The nuclear magnetic resonance spectrum, high resolution mass spectrum and high performance liquid chromatography data of the obtained product were as follows: 2-Adamantyl 2-hydroxy-6-methoxyl-1-oxo-2,3-dihydro-1 H -indene-2-carboxylate (4b) colorless oil; 28.8mg; 81%; 1 H NMR (600 MHz, Chloroform-d) δ7.41 (d, J = 8.3 Hz, 1H), 7.29 – 7.27 (m, 1H), 7.25 (d, J = 2.5 Hz, 1H), 4.98(t, J = 3.5 Hz, 1H), 3.86 (s, 3H), 3.65 (d, J = 16.6 Hz, 1H), 3.23 (d, J=16.6 Hz, 1H), 1.95 (d, J = 3.7 Hz, 1H), 1.88 (d, J = 3.5 Hz, 1H), 1.83 – 1.79(m, 3H), 1.74 – 1.68 (m, 3H), 1.62 (td, J = 5.3, 4.6, 2.3 Hz, 2H), 1.50 (dt,J = 12.9, 3.0 Hz, 2H), 1.45 – 1.41 (m, 2H). 2 C NMR (151 MHz, Chloroform-d) δ200.06, 169.77, 158.85, 144.01, 134.26, 126.18, 126.01, 124.99, 124.24,105.25, 80.58, 78.76, 54.70, 37.99, 36.12, 35.12, 35.04, 30.92, 30.77, 30.54,30.36. HRMS (ESI) calcd for C 21 H 24 O5 ([M+Na] + ) = 379.1516, found:379.1499. HPLCconditions: Chiralcel AD-H column (250 × 4.6 mm), hexane / i -PrOH = 80 / 20, 1mL / min, 254nm, τR(major) = 12.73 min, τR(minor) = 14.74 min. Application Example 3:

[0060] To a dry 15 mL high pressure sealed tube was added 7.1 mg chiral ligand, 3.49 mg Cu(OTf)2, 2 mL anhydrous toluene, the tube was replaced with argon and then the complexation was carried out at 50 °C for 30 min. After the complexation, 33.93 mg 3c and 8.48 mg TX-HCPs4 were added, and the reaction was placed in a -15 °C cold bath for 13 h. After the reaction, the reaction solution was chromatographed using a silica gel column with ethyl acetate: petroleum ether = 1:20 as the eluent. The hydroxylated product 4c was isolated in 75% yield with 66% ee.

[0061]

[0062] The product obtained had the following NMR, HRMS and HPLC data: 2-Adamantyl 2-hydroxy-5-methoxyl-1-oxo-2,3-dihydro-1 H -indene-2-carboxylate (4c) colorless oil; 26.7 mg; 75%; 1 H NMR (600 MHz, Chloroform-d) δ 7.74 (dd, J = 11.5, 8.5 Hz, 1H), 6.94 (ddt, J = 14.1, 4.3, 2.3 Hz, 2H), 5.00 (dt, J = 55.3, 3.6 Hz, 1H), 3.91 (d, J = 3.1 Hz, 4H), 3.64 (dd, J = 22.4, 17.3 Hz, 1H), 3.23 (d, J = 17.0 Hz, 1H), 1.93 (d, J = 4.5 Hz, 1H), 1.87 (d, J = 4.1 Hz, 1H), 1.79 (ddt, J = 14.4, 5.8, 2.7 Hz, 3H), 1.70 (dt, J = 13.4, 2.6 Hz, 2H), 1.64 – 1.59 (m, 3H), 1.52 (dd, J = 12.7, 3.2 Hz, 1H), 1.48 – 1.39 (m, 2H), 1.36 (dt, J = 5.0, 2.7 Hz, 1H). 13C NMR (151 MHz, Chloroform-d) δ 198.93, 170.90, 166.30, 155.14, 127.38, 126.91, 115.96, 109.82, 109.63, 91.01, 81.15, 39.52, 37.13, 31.78. HRMS (ESI) calcd for C 21 H 24 O5 ([M+Na] + ) = 379.1516,found:379.1503. HPLC conditions: Chiralcel AD-H column (250 × 4.6 mm),hexane / i-PrOH = 80 / 20, 1 mL / min, 254nm, τR(major) = 15.88 min, τR(minor) =18.29 min. Application Example 4:

[0063] Into a dry 15 mL high pressure sealed tube, 7.1 mg chiral ligand, 3.49 mg Cu(OTf)2, 2 mL anhydrous toluene were added, the gas in the tube was replaced by argon, then the complexation was carried out at 50 °C for 30 min, after the complexation, 32.33 mg 3d and 8.08 mg TX-HCPs4 were added, the reaction was placed in a -15 °C cold trap for 13 h, after the reaction, the reaction solution was chromatographed using a silica gel column, the eluent was ethyl acetate: petroleum ether = 1:20, the hydroxylated product 4d was separated, the yield was 76%, and the ee value was 67%.

[0064]

[0065] The nuclear magnetic resonance spectrum, high resolution mass spectrum and high performance liquid chromatography data of the obtained product are: 2-Adamantyl 2-hydroxy-6-methyl-1-oxo-2,3-dihydro-1H-indene-2-carboxylate (4d) white solid; m.p.=95-97℃; 25.8mg; 76%; 1H NMR (600 MHz, Chloroform-d) δ 7.59 (s, 1H), 7.47 (d, J = 6.0 Hz, 1H), 7.38 (d, J = 7.8 Hz, 1H), 4.95 (t, J = 3.6 Hz, 1H), 3.99 (s, 1H), 3.66 (d, J = 16.8 Hz, 1H), 3.23 (d, J = 16.8 Hz, 1H), 2.41 (s, 3H), 1.94 - 1.90 (m, 1H), 1.85 (d, J = 4.1 Hz, 1H), 1.82 - 1.76 (m, 3H), 1.73 - 1.64 (m, 3H), 1.63 (s, 2H), 1.49 - 1.45 (m, 1H), 1.40 (dd, J = 12.7, 2.7 Hz, 1H), 1.32 (dt, J = 6.7, 2.8 Hz, 2H). 13 C NMR (151 MHz, Chloroform-d) δ 201.10, 170.80, 149.46, 138.08, 137.14, 134.24, 125.93, 124.93, 79.71, 39.25, 37.13, 36.11, 36.03, 31.76, 31.51, 31.32, 26.89, 26.73, 21.05. HRMS (ESI) calcd for C20H22O4 ([M+Na] + ) = 363.1567, found: 363.1571. HPLC conditions: Chiralcel AD-H column (250 × 4.6 mm), hexane / i-PrOH = 80 / 20, 1 mL / min, 254 nm, τR(major) = 9.00 min, τR(minor) = 12.03 min. Application Example 5:

[0066] Into a dry 15 mL high pressure sealed tube, 7.1 mg of chiral ligand, 3.49 mg of Cu(OTf)2, 2 mL of anhydrous toluene were added, the tube was replaced with argon and then the complexation was carried out at 50 °C for 30 min. After the complexation, 32.33 mg of 3e and 8.08 mg of TX-HCPs4 were added, and the reaction was placed in a -15 °C cold bath for 13 h. After the reaction, the reaction solution was chromatographed using a silica gel column, and the eluent was ethyl acetate: petroleum ether = 1:20. The hydroxylated product 4e was separated in a yield of 71% and an ee value of 73%.

[0067]

[0068] The nuclear magnetic resonance spectrum, high resolution mass spectrum and high performance liquid chromatography data of the product obtained are as follows: 2-Adamantyl 2-hydroxy-5-methyl-1-oxo-2,3-dihydro-1 H -indene-2-carboxylate (4e) white solid; m.p.=123-124.5℃; 24.1mg; 71%; 1 H NMR (600 MHz, Chloroform-d) δ 7.68 (dd, J = 7.7, 1.9 Hz, 1H), 7.29 (s, 1H), 7.21 (d, J = 7.9 Hz, 1H), 4.94 (d, J = 3.6 Hz, 1H), 4.06 (s, 1H), 3.65 (d, J = 16.9 Hz, 1H), 3.23 (d, J = 16.9 Hz, 1H), 2.45 (d, J = 1.8 Hz, 3H), 1.91 (s, 1H), 1.85 (s, 1H), 1.80 – 1.73 (m, 3H), 1.69 (d, J = 14.8 Hz, 2H), 1.62 (s, 2H), 1.59 – 1.56 (m, 1H), 1.46 (d, J = 12.9 Hz, 1H), 1.39 (d, J = 12.6 Hz, 1H), 1.32 (s, 2H). 13C NMR (151 MHz, Chloroform-d) δ 199.46, 169.85, 151.56, 146.43, 130.80, 128.29, 125.61, 123.92, 80.15, 78.67, 38.44, 36.14, 35.13, 35.03, 30.77, 30.53, 30.51, 30.33, 25.90, 25.75, 21.21. HRMS (ESI) calcd for C21H24O4 ([M+Na] + ) = 363.1567, found:363.1571. HPLC conditions: Chiralcel AD-H column (250× 4.6 mm), hexane / i -PrOH = 80 / 20, 1 mL / min, 254nm, τR(major) = 11.27 min, τR(minor) = 14.69 min. Application Example 6:

[0069] To a dry 15 mL high pressure sealed tube was added 7.1 mg chiral ligand, 3.49 mg Cu(OTf)2, 2 mL anhydrous toluene, the tube was replaced with argon and then ligated at 50 °C for 30 min, after the end of the ligation, 32.73 mg 3f and 8.18 mg TX-HCPs4 were added, and the reaction was placed in a -15 °C cold trap for 13 h, after the end of the reaction, the reaction solution was chromatographed using a silica gel column, eluent was ethyl acetate: petroleum ether = 1:20, the hydroxylated product 4f was separated, the yield was 83%, and the ee value was 90%.

[0070]

[0071] The nuclear magnetic resonance spectrum, high resolution mass spectrum and high performance liquid chromatography data of the product obtained were: 2-Adamantanyl 2-hydroxy-6-fluoro-1-oxo-2,3-dihydro-1 H -indene-2-carboxylate (4f) colorless oil; 28.5mg; 83%; 1H NMR (600 MHz, Chloroform-d) δ 7.48 (dd, J = 8.5, 4.5 Hz, 1H), 7.44 (dd, J = 7.2, 2.6 Hz, 1H), 7.38 (td, J = 8.5, 2.6 Hz, 1H), 4.06 (s, 1H), 3.66 (d, J = 16.7 Hz, 1H), 3.25 (d, J = 13.8 Hz, 1H), 1.92 (d, J = 2.8 Hz, 1H), 1.87–1.84 (m, 1H), 1.79 (dt, J = 12.6, 2.6 Hz, 3H), 1.69 (ddd, J = 19.0, 10.2, 3.5 Hz, 3H), 1.63 (d, J = 3.7 Hz, 2H), 1.42 (d, J = 3.1 Hz, 2H), 1.35 (d, J = 12.9 Hz, 1H), 1.29–1.25 (m, 2H). 13 CNMR (151 MHz, Chloroform-d) δ 199.26, 169.34, 162.34, 160.69, 146.47, 134.88, 134.83, 126.76, 126.71, 122.65, 122.50, 109.89, 109.74, 80.56, 79.04, 38.06, 36.07, 35.10, 35.01, 30.77, 30.56, 30.52, 30.36. HRMS (ESI) calcd for C 20 H 21 FO4([M+Na] + ) = 367.1317, found:367.1305. HPLC conditions: Chiralcel AD-H column(250 × 4.6 mm), hexane / i-PrOH = 80 / 20, 1 mL / min, 254nm, τR(major) = 9.22min, τR(minor) = 12.01 min. Application Example 7:

[0072] Into a dry 15 mL high pressure sealed tube, 7.1 mg chiral ligand, 3.49 mg Cu(OTf)2, 2 mL anhydrous toluene, replace the gas in the tube with argon, then coordinate for 30 min at 50 °C, after coordination, add 32.73 mg 3g and 8.18 mg TX-HCPs4, place the reaction in a -15 °C cold bath for 13 h, after the reaction is completed, the reaction liquid is chromatographed using a silica gel column, eluent is ethyl acetate: petroleum ether = 1:20, isolate the hydroxylated product 4g, its yield is 87%, ee value is 81%.

[0073]

[0074] The nuclear magnetic resonance spectrum, high resolution mass spectrum and high performance liquid chromatography data of the product obtained are: 2-Adamantanyl 2-hydroxy-5-fluoro-1-oxo-2,3-dihydro-1 H -indene-2-carboxylate (4g) colorless oil; 29.7mg; 86.6%; 1 H NMR (300 MHz, )δ7.81 (dd, J= 4.2, 2.6 Hz), 7.17 (dd, J = 4.2, 1.1 Hz), 7.12 (td, J = 4.3, 1.1 Hz), 4.96(t, J = 1.7 Hz), 4.08, 3.69 (d, J = 8.6 Hz), 3.28 (d, J = 8.6 Hz), 1.91,1.85, 1.77 (t, J = 1.7 Hz), 1.67 (d, J = 7.0 Hz), 1.62, 1.46 (d, J = 6.5 Hz),1.41, 1.32. 13 C NMR (151 MHz, Chloroform-d) δ 198.11, 169.37, 167.67, 166.71,165.95, 153.99 (d, J = 21.3 Hz), 129.85 (d, J = 7.7 Hz), 126.48 (d, J = 21.3Hz), 115.50, 115.35, 112.23, 112.08, 78.97, 67.18, 36.09, 35.11, 35.02,30.78, 30.55 (d, J = 17.9 Hz), 30.39, 29.41. HRMS (ESI) calcd for C20 H 21 FO4 ([M+Na] + ) = 367.1317, found:367.1312. HPLC conditions: Chiralcel AD-H column(250×4.6 mm), hexane / i-PrOH = 80 / 20, 1 mL / min, 254nm, τR(major) = 10.03 min,τR(minor) = 12.18 min. Application Example 8:

[0075] Into a dry 15 mL high pressure sealed tube, 7.1 mg chiral ligand, 3.49 mg Cu(OTf)2, 2 mL dry toluene were added, the gas in the tube was replaced by argon, then the complexation was carried out at 50 °C for 30 min, after the complexation, 34.33 mg 3h and 8.58 mg TX-HCPs4 were added, the reaction was placed in a -15 °C cold trap for 13 h, after the reaction, the reaction liquid was chromatographed using a silica gel column, the eluent was ethyl acetate: petroleum ether = 1:20, the hydroxylated product 4h was separated, the yield was 91%, the ee value was 87%.

[0076]

[0077] The nuclear magnetic resonance spectrum, high resolution mass spectrum and high performance liquid chromatography data of the product obtained are: 2-Adamantanyl 2-hydroxy-6-chloro-1-oxo-2,3-dihydro-1 H -indene-2-carboxylate (4h) white solid; m.p.=110-112℃; 32.8mg; 91.2%; 1H NMR (600 MHz, Chloroform-d) 7.73 (d, J = 8.2 Hz, 1H), 7.50 (s, 1H), 7.40 (dd, J = 8.2, 1.8 Hz, 1H), 4.96 (t, J = 3.5 Hz, 1H), 4.04 (s, 1H), 3.67 (d, J = 17.1 Hz, 1H), 3.27 (d, J = 17.2 Hz, 1H), 1.92 (s, 1H), 1.86 (s, 1H), 1.78 (ddt, J = 15.3, 12.5, 3.1 Hz, 3H), 1.69 (ddd, J = 16.7, 12.6, 2.9 Hz, 2H), 1.63 (d, J = 11.4 Hz, 3H), 1.44 (s, 2H), 1.36 (d, J = 13.1 Hz, 1H), 1.31 - 1.27 (m, 1H). 13 C NMR (151 MHz, Chloroform-d) δ 199.87, 170.25, 150.05, 135.86, 135.60, 134.43, 127.49, 124.70, 81.26, 80.09, 39.16, 37.05, 36.09, 36.00, 31.75, 31.56, 31.51, 31.37, 26.82, 26.69. HRMS (ESI) calcd for C 20 H 21 ClO4 ([M+Na] + ) =383.1021, found:367.1006. HPLC conditions: Chiralcel AD-H column (250 × 4.6mm), hexane / i-PrOH = 80 / 20, 1 mL / min, 254nm, τR(major) = 9.53 min, τR(minor)= 12.84 min. Application Example 9:

[0078] Into a dry 15 mL high pressure sealed tube, 7.1 mg of chiral ligand, 3.49 mg of Cu(OTf)2, 2 mL of anhydrous toluene were added, the gas in the tube was replaced by argon, and then the coordination was carried out at 50°C for 30 min. After the coordination was completed, 34.33 mg of 3i and 8.58 mg of TX-HCPs4 were added, and the reaction was placed in a -15°C cold trap for 13 h. After the reaction was completed, the reaction solution was chromatographed using a silica gel column, and the eluent was ethyl acetate: petroleum ether = 1:20. The hydroxylated product 4i was separated in a yield of 94% and an ee value of 89%.

[0079]

[0080] The nuclear magnetic resonance spectrum, high resolution mass spectrum and high performance liquid chromatography data of the obtained product are as follows: 2-Adamantanyl 2-hydroxy-5-chloro-1-oxo-2,3-dihydro-1 H -indene-2-carboxylate (4i) white solid; m.p.=143-145℃; 33.9mg; 94.3%; 1 H NMR (600 MHz, Chloroform-d) δ 7.76 (d, J = 2.2 Hz, 1H), 7.61 (dd, J = 8.2, 2.2 Hz, 1H), 7.45 (d, J = 8.1 Hz, 1H), 4.96 (t, J = 3.5 Hz, 1H), 4.06 (s, 1H), 3.66 (d, J = 17.1 Hz, 1H), 3.25 (d, J = 17.1 Hz, 1H), 1.92 (s, 1H), 1.86 (d, J = 3.7 Hz, 1H), 1.78 (td, J = 15.7, 14.9, 3.1 Hz, 3H), 1.72–1.67 (m, 2H), 1.64 (s, 3H), 1.43 (d, J = 3.0 Hz, 2H), 1.31–1.22 (m, 2H). 13C NMR (151 MHz, Chloroform-d) δ 199.60, 170.31, 153.40, 142.56, 132.56, 128.92, 126.54, 126.11, 80.91, 80.07, 39.26, 37.06, 36.09, 36.01, 31.76, 31.56, 31.50, 31.37. HRMS (ESI) calcd for C 20 H 21 ClO4 ([M+Na] + ) = 383.1021, found:367.1008. HPLC conditions: Chiralcel AD-H column (250 × 4.6 mm), hexane / i-PrOH = 80 / 20, 1 mL / min, 254nm, τR(major) =11.12 min, τR(minor) = 13.59 min. Application Example 10:

[0081] Into a dry 15 mL high pressure sealed tube, 7.1 mg chiral ligand, 3.49 mg Cu(OTf)2, 2 mL anhydrous toluene were added, the gas in the tube was replaced by argon, then the coordination was carried out at 50°C for 30 min, after the end of the coordination, 38.72 mg 3j and 9.68 mg TX-HCPs4 were added, and the reaction was placed in a-15°C cold trap for 13 h, after the end of the reaction, the reaction liquid was chromatographed using a silica gel column, the eluent was ethyl acetate: petroleum ether = 1:20, and the hydroxylated product 4j was separated, the yield was 96%, and the ee value was 88%.

[0082]

[0083] The nuclear magnetic resonance spectrum, high resolution mass spectrum and high performance liquid chromatography data of the obtained product were as follows: 2-Adamantyl 2-hydroxy-6-bromine-1-oxo-2,3-dihydro-1 H -indene-2-carboxylate (4j) white solid; 110.6-112.6°C; 38.8mg; 96.2%; 1H NMR (600 MHz, Chloroform-d) δ 7.92 (d, J = 1.8 Hz, 1H), 7.76 (dd, J = 8.1, 2.0 Hz, 1H), 7.39 (d, J = 8.1 Hz, 1H), 4.98 - 4.94 (m, 1H), 4.04 (s, 1H), 3.65 (d, J = 17.1 Hz, 1H), 3.22 (d, J = 17.1 Hz, 1H), 1.92 (d, J = 4.4 Hz, 1H), 1.85 (d, J = 6.7 Hz, 1H), 1.82 - 1.77 (m, 3H), 1.69 (t, J = 13.9 Hz, 3H), 1.64 (s, 2H), 1.43 (s, 2H), 1.37 (d, J = 13.0 Hz, 1H), 1.30 - 1.26 (m, 1H). 13 C NMR (151 MHz, Chloroform-d) δ 199.66, 170.22, 150.50, 138.60, 135.91, 127.83, 127.79, 122.12, 81.13, 80.11, 39.21, 37.06, 36.10, 36.01, 31.77, 31.57, 31.52, 31.37, 26.91, 26.84, 26.70. HRMS (ESI) calcd for C 20 H 21 BrO4([M+Na] + ) = 427.0516, found: 367.0501. HPLC conditions: Chiralcel AD-H column (250 x 4.6 mm), hexane / i-PrOH = 80 / 20, 1 mL / min, 254 nm, τR(major) = 9.77 min, τR(minor) = 13.00 min. Example 11:

[0084] Into a dry 15 mL high pressure sealed tube, 7.1 mg chiral ligand, 3.49 mg Cu(OTf)2, 2 mL anhydrous toluene were added, the tube was replaced with argon and then the complexation was carried out at 50 °C for 30 min. After the complexation, 38.72 mg 3k and 9.68 mg TX-HCPs4 were added, and the reaction was placed in a -15 °C cold bath for 13 h. After the reaction, the reaction solution was chromatographed using a silica gel column with ethyl acetate: petroleum ether = 1:20 as the eluent. The hydroxylated product 4k was isolated in 95% yield with an ee value of 77%.

[0085]

[0086] The nuclear magnetic resonance spectrum, high resolution mass spectrum and high performance liquid chromatography data of the product obtained are as follows: 2-Adamantyl 2-hydroxy-5-bromine-1-oxo-2,3-dihydro-1 H -indene-2-carboxylate (4k) white solid; 152.7-153.7 °C; 38.3 mg; 95%; 1 H NMR (600 MHz, Chloroform-d) δ 7.69 (s, 1H), 7.66 (d, J = 8.1 Hz, 1H), 7.57 (dd, J = 8.2, 1.6 Hz, 1H), 4.96 (t, J = 3.5 Hz, 1H), 4.01 (s, 1H), 3.68 (d, J = 17.2 Hz, 1H), 3.27 (d, J = 17.1 Hz, 1H), 1.92 (t, J = 3.6 Hz, 1H), 1.88–1.85 (m, 1H), 1.83–1.77 (m, 3H), 1.69 (td, J = 13.6, 13.1, 3.1 Hz, 3H), 1.64 (s, 2H), 1.44 (s, 2H), 1.38 (s, 1H), 1.30 (dd, J = 12.9, 2.8 Hz, 1H). 13C NMR (151 MHz, Chloroform-d) δ 198.84, 169.28, 152.47, 131.96, 130.79, 130.41, 128.64, 125.15, 79.11, 38.20, 36.07, 35.11, 35.02, 30.77, 30.58, 30.51, 30.38, 25.85, 25.70. HRMS (ESI) calcd for C 20 H 21 BrO4 ([M+Na] + ) = 427.0516, found:367.0497.HPLC conditions: Chiralcel AD-H column (250×4.6 mm), hexane / i-PrOH = 80 / 20,1 mL / min, 254nm, τR(major) = 12.00 min, τR(minor) = 15.05 min. Application Example 12:

[0087] Into a dry 15 mL high pressure sealed tube, 7.1 mg chiral ligand, 3.49 mg Cu(OTf)2, 2 mL anhydrous toluene were added, the gas in the tube was replaced by argon, then the coordination was carried out at 50 °C for 30 min, after the coordination was completed, 38.72 mg 3l and 9.68 mg TX-HCPs4 were added, and the reaction was placed in a -15 °C cold trap for reaction for 13 h, after the reaction was completed, the reaction solution was chromatographed using a silica gel column, eluent was ethyl acetate: petroleum ether = 1:20, the hydroxylated product 4l was separated, the yield was 95%, and the ee value was 74%.

[0088]

[0089] The nuclear magnetic resonance spectrum, high resolution mass spectrum and high performance liquid chromatography data of the obtained product were as follows: 2-Adamantyl 2-hydroxy-4-bromine-1-oxo-2,3-dihydro-1 H -indene-2-carboxylate (4l) white solid; 157-159 °C; 38.2 mg; 94.8%; 1H NMR (600 MHz, Chloroform-d) δ 7.82 (d, J = 7.8 Hz, 1H), 7.75 (d, J = 7.5 Hz, 1H), 7.32 (t, J = 7.7 Hz, 1H), 4.95 (t, J = 3.5 Hz, 1H), 4.09 (s, 1H), 3.67 (d, J = 17.4 Hz, 1H), 3.20 (d, J = 17.4 Hz, 1H), 1.81 (dd, J = 6.8, 3.5 Hz, 2H), 1.79–1.73 (m, 3H), 1.69 (dd, J = 17.7, 4.1 Hz, 2H), 1.63 (s, 2H), 1.60–1.57 (m, 1H), 1.44 (s, 2H), 1.32 (d, J = 12.9 Hz, 1H), 1.23 (t, J = 11.7 Hz, 2H). 13 C NMR (151 MHz, Chloroform-d) δ 200.42, 170.16, 151.69, 138.52, 136.19, 129.74, 123.72, 121.67, 80.93, 80.05, 40.66, 37.07, 36.08, 36.01, 31.76, 31.52, 31.50, 31.35, 26.91, 26.85, 26.69. HRMS (ESI) calcd for C 20 H 21 BrO4 ([M+Na] + ) = 427.0516, found: 367.0502. HPLC conditions: Chiralcel AD-H column (250 x 4.6 mm), hexane / i-PrOH = 80 / 20, 1 mL / min, 254 nm, τR(major) = 9.57 min, τR(minor) = 11.27 min. Application Example 13:

[0090] 7.1 mg of chiral ligand, 3.49 mg of Cu(OTf)2, and 2 mL of anhydrous toluene were added to a dry 15 mL high-pressure sealed tube. The gas in the tube was replaced with argon, and coordination was carried out at 50 °C for 30 min. After coordination, 30.94 mg of 3m and 7.73 mg of TX-HCPs4 were added, and the reaction was carried out in a -15 °C cold trap for 13 h. After the reaction, the reaction solution was subjected to silica gel column chromatography with ethyl acetate:petroleum ether = 1:20 as the eluent. The hydroxylated product 4m was obtained with a yield of 89% and an ee value of 51%.

[0091]

[0092] The nuclear magnetic resonance spectrum, high-resolution mass spectrometry, and high-performance liquid chromatography data of the obtained product are as follows: 1-Adamantyl 2-hydroxy-1-indanone-2-carboxylate (4m) white solid; mp=81-83℃; 29.1mg, 89.4% 1 H NMR (600 MHz, Chloroform-d)δ7.79 (d, J = 7.6 Hz,1H), 7.64 (t, J = 7.5 Hz, 1H), 7.47 (d, J = 7.6 Hz, 1H), 7.41 (t, J = 7.5 Hz,1H), 3.65 (d, J = 17.0 Hz, 1H), 3.21 (d, J = 17.0 Hz, 1H), 2.11 (s, 4H), 1.96(s, 4H), 1.59 (s, 7H). HRMS (ESI) calcd for C 20 H 22 O4 ([M+Na) + ) = 349.1411, found: 349.1405. HPLC conditions: Chiralcel AD-H column (250×4.6 mm), hexane / i-PrOH = 80 / 20, 1 mL / min, 254nm, τR(major) = 9.93 min, τR(minor) =15.08 min. Application Example 14:

[0093] Into a dry 15 mL pressure tube, 7.1 mg of chiral ligand, 3.49 mg of Cu(OTf)2, 2 mL of anhydrous toluene were added, the gas in the tube was replaced by argon, then the coordination was carried out at 50°C for 30 min, after the coordination, 18.96 mg of 3n and 4.74 mg of TX-HCPs4 were added, the reaction was placed in a -15°C cold sink for 13 h, after the reaction, the reaction liquid was chromatographed by using a silica gel column, the eluent was ethyl acetate: petroleum ether = 1:20, the hydroxylated product 4n was separated, the yield was 90%, and the ee value was 65%.

[0094]

[0095] The nuclear magnetic resonance spectrum and high performance liquid chromatography data of the obtained product are as follows: Methyl 2-hydroxy-1-oxo-2,3-dihydro-1 H -indene-2-carboxylate (4n) white solid; m.p. = 133-135°C; 18.5 mg, 90% 1 H NMR (600 MHz, Chloroform-d) 1 H NMR (400MHz, Chloroform-d) δ 7.79 (d, J = 7.7 Hz, 1H), 7.66 (t, J = 7.5 Hz, 1H), 7.49(d, J = 7.8 Hz, 1H), 7.42 (t, J = 7.5 Hz, 1H), 4.05 (d, J = 1.9 Hz, 1H),3.77–3.68 (m, 4H), 3.25 (d, J = 17.3 Hz, 1H). HPLC conditions: Chiralcel OD-Hcolumn (250×4.6 mm), hexane / i-PrOH = 90 / 10, 1 mL / min, 254nm, τR(major) =10.88 min, τR(minor) =13.16 min. The details of the present application are known technologies.

Claims

1. An ultracross-linked photosensitive material, characterized in that the material has the following structural formula: ； wherein, R 1 is a 4DPAIPN, 4CzIPN, anthraquinone or thioxanthone building block; R 2 is a 1,4-p-xylylene, 1,3,5-trimethylbenzene or 1,4-p-xylylene diphenyl building block. The solid lines represent carbon-carbon bonds, R 2 connected building blocks can be other R 1 or R 2 but R 1 can only be connected to R 2 and this structure is repeated to ultimately form the hypercrosslinked material.

2. The method for preparing the hypercrosslinked photosensitive material as described in claim 1, characterized in that, comprising the following steps: Step one, adding photosensitive molecules, cross-linking agent and Lewis acid into the first solvent, then reacting at 60-100℃ for 18-26 hours in an inert atmosphere; the reaction solution is filtered, the solid crude product is washed first, then is washed by Soxhlet extraction for 10-24 hours to obtain the crude product of the ultracross-linked photosensitive material; wherein the molar ratio of photosensitive molecules to cross-linking agent is 1:1-8; the molar ratio of Lewis acid to photosensitive molecules is 1-5:1; 0.3mmol~1.2mmol photosensitive molecules are added per 30 mL of the first solvent; the photosensitive molecules are thioxanthone, anthraquinone, 4CzIPN or 4DPAIPN; the cross-linking agent is p-dichlorobenzyl, 1, 4-di(bromomethyl)benzene, 1, 3, 5-tri(bromomethyl)benzene, or biphenyl dichlorobenzyl; the Lewis acid is anhydrous ferric chloride or anhydrous aluminum chloride; the first solvent is 1, 2-dichloroethane or dichloromethane; Step two, drying the crude product of the ultracross-linked photosensitive material obtained in the previous step at 60-100℃ for 10-24 hours to obtain the ultracross-linked photosensitive material.

3. The method for preparing the hypercrosslinked photosensitive material as described in claim 2, characterized in that, The inert gas is argon or nitrogen.

4. The method of claim 2, wherein the step of The washing is washing with 0.5-2mol hydrochloric acid, water, methanol, dichloromethane respectively; the Soxhlet extraction is carried out with 0.5-2mol hydrochloric acid, water, mixed solvent respectively; the mixed solvent is dichloromethane and methanol, the volume ratio of which is 1:

1.

5. Use of an overcrosslinked photoreactive material according to claim 1, characterized in that For preparing optically pure α-hydroxylate in the asymmetric α-hydroxylation reaction of catalytic β-keto ester.

6. Use of an overcrosslinked photoreactive material according to claim 5, characterized in that comprising the following steps: Step one, adding chiral ligand, metal catalyst and second solvent into a high-pressure sealed tube in sequence, sealing and filling with argon or nitrogen, stirring at 20~50℃ for 0.5~2 hours to obtain a complex; Step two, then adding β-keto ester, ultracross-linked photosensitive material in sequence, filling with 1-3 atmospheres of oxygen, stirring at -30℃~30℃ and under light for 2~30 hours to obtain the α-hydroxylate of β-keto ester; wherein 7-10 mg of chiral ligand, 3-7 mg of metal catalyst, 20 -35 mg of β-keto ester, and 6-9 mg of ultracross-linked photosensitive material are added per 2 mL of the second solvent; The second solvent is toluene, xylene, dichloromethane, methanol, acetonitrile, tetrahydrofuran or methyl tert-butyl ether; The chiral ligand is a salen ligand; The metal catalyst is Cu(OTf)2, Ni(OTf)2, Zn(OTf)2, Fe(OTf)2, Zr(acac)2 or Cu(OAc)2; The β-keto ester is 1-indanone-2-carboxylic acid (2-adamantane) ester, 1-indanone-2-carboxylic acid (methyl) ester or 1-indanone-2-carboxylic acid (1-adamantane) ester with different substituents such as methyl, methoxy, fluorine atom, chlorine atom, bromine atom, etc.

7. Use of a super-crosslinked photoreactive material according to claim 6, characterized in that The structure of the chiral ligand L is as follows: 。

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