CN108516937B - Method for preparing chiral alpha-hydroxy-beta-keto ester compound by visible light-initiated aerobic Salan-copper catalyst - Google Patents
Method for preparing chiral alpha-hydroxy-beta-keto ester compound by visible light-initiated aerobic Salan-copper catalyst Download PDFInfo
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Abstract
The invention provides a method for preparing a chiral alpha-hydroxy-beta-keto ester compound by using a visible light-initiated aerobic Salan-copper catalyst, belonging to the technical field of photocatalytic asymmetric synthesis. The method comprises the steps that in an aromatic hydrocarbon solvent, a visible light irradiates a photosensitizer to excite oxygen to be active singlet oxygen, the singlet oxygen attacks a beta-keto ester compound activated by a chiral Salan-copper catalyst to carry out asymmetric catalytic oxidation reaction, and the alpha-hydroxy-beta-keto ester compound with optical activity is prepared. The invention uses Salan-copper catalyst which is easy to synthesize, low in price and stable in property, can effectively prepare the chiral alpha-hydroxy-beta-keto ester compound, and obtains very high yield and very good enantioselectivity.
Description
Technical Field
The invention belongs to the technical field of photocatalytic asymmetric synthesis, and discloses a method for preparing a chiral alpha-hydroxy-beta-keto ester compound by using oxygen or air as an oxidant or a final oxygen atom source, exciting the oxygen to form reactive singlet oxygen under the irradiation of visible light, and using a (1S,2S) -1, 2-diphenyldiamine derivative as a ligand and a complex with copper trifluoromethanesulfonate as a central metal as a catalyst.
Background
Some alpha-hydroxy-beta-keto ester compounds with optical activity are important structural units and widely exist in natural products, and are used as intermediates for preparing medicines, pesticides and fine chemicals. The most ideal, simple and quick method for preparing the chiral alpha-hydroxy-beta-keto ester compound is to enantioselectively catalyze and oxidize the beta-keto ester compound. Davis firstly reports a method for obtaining chiral alpha-hydroxy-beta-dicarbonyl compound by using Davis reagent in 1981 (Tetrahedron Lett.1981,22, 4385-.
In recent years, researchers have reported a number of asymmetric synthetic methods for chiral α -hydroxy- β -keto ester compounds, including 1) organic catalysis; 2) a metal complex. For organic catalysis, WO 03/040083 and J.org.chem.2004,69,8165-8167 disclose a process for preparing chiral α -hydroxy- β -dicarbonyl compounds using cinchona alkaloids and derivatives thereof as organic catalysts and organic peroxides as oxidizing agents, wherein the yield of the oxidation products is generally 80-90% and the corresponding selectivity is generally 50-80% ee. The aryloxyalcohol catalysts (tetrahedron.2012,38, 7973-. In addition, in the context of metal complexes, the literature (proc. natl. acad. sci. u. s.a.2004,101, 5810-5814) for the first time reports metal complexes of tartaric acid-derived chiral ligands coordinated to tetravalent Ti; complexes of tartaric acid derivatives coordinated with Mg reported by the Feng group in recent years are catalysts (adv.synth.catal.2013,355, 1924-1930); complexes of salen ligands with Fe reported by Che as catalysts (chem. commun.2014,50,7870-7873) also gave some better results. However, the oxidizing agent used in these processes is generally an azaoxetane of complex structure. These factors limit the application of the two types of methods described above. There is still a need for improved more economical and environmentally friendly methods of preparation for the preparation of chiral alpha-hydroxy-beta-keto ester compounds. In recent years, oxygen or air has been developed as an oxidant or a source of final oxygen atoms, and in particular, catalytic oxidation of organic compounds by visible light activation of oxygen has been regarded by chemists. The inventor subject group autonomously develops the synergistic effect of an organic catalyst cinchona alkaloid derivative and a tetraphenylporphyrin photosensitizer (chem.asian J.2012,7,2019-2023), and the xiaonjing subject group catalyzes an oxidation reaction by using a Box-Ni catalyst and the photosensitizer (J.Am.chem.Soc.2017,139, 63-66). However, these methods have limitations on the range of reactants, limiting their widespread use. Thus, the present invention provides a more sustainable synthetic approach to chiral α -hydroxy- β -keto ester compounds in terms of energy and environmental protection.
Disclosure of Invention
The invention aims to provide a visible light catalytic beta-keto ester compound asymmetric alpha-hydroxylation reaction method taking oxygen or air as an oxidant or a final oxygen atom source. A copper complex taking chiral (1S,2S) -1, 2-diphenyldiamine derivatives as ligands (Salan) as a catalyst, and a photosensitizer tetraphenylporphyrin excited oxygen as active singlet oxygen to interact with a beta-keto ester compound (III) under the irradiation of visible light to carry out asymmetric alpha-hydroxylation reaction to prepare an alpha-hydroxy-beta-keto ester compound (IV).
The technical scheme of the invention is as follows:
a method for preparing chiral alpha-hydroxy-beta-keto ester compound by using visible light to initiate aerobic Salan-copper catalyst comprises the following steps: in an aromatic hydrocarbon solvent, visible light irradiates a photosensitizer to excite oxygen to be singlet oxygen, the singlet oxygen attacks the beta-keto ester compound activated by the chiral Salan-copper catalyst to carry out asymmetric catalytic oxidation reaction, and the alpha-hydroxy-beta-keto ester compound with optical activity is prepared.
The chiral Salan-copper catalyst is a (1S,2S) -1, 2-diphenyldiamine derivative Salan-copper catalyst, and the structure of the catalyst is shown as a formula I:
wherein the complex is copper chloride, copper perchlorate, copper acetate, copper acetylacetonate or copper trifluoromethanesulfonate; the ligand is of formula II:
wherein, (1S,2S) -1, 2-diphenyldiamine is a connecting chain; r 'and R' are halogen, NO2Cyano, C2-C8Alkyl radical, C5-C6Cycloalkyl radical, C2-C8Alkoxy, adamantyl, benzene ring, five-membered aromatic heterocycle, six-membered aromatic heterocycle or 1-naphthyl, and R' are the same or different.
The photosensitizer is tetraphenylporphyrin, copper tetraphenylporphyrin, phthalocyanine, copper phthalocyanine, eosin E, eosin Y, rose bengal, acetophenone or benzophenone.
The beta-ketoester compound is of formula III:
wherein R is1、R2And R3Is a hydrogen atom, halogen, alkyl or alkoxy, R1、R2And R3The same or different; r4Is alkyl, cycloalkyl, aromatic ring or benzyl; n is 1 or 2.
The alpha-hydroxy-beta-keto ester compound is shown as a formula IV:
wherein R is1、R2And R3Is a hydrogen atom, halogen, alkyl or alkoxy, R1、R2And R3The same or different; r4Is alkyl, cycloalkyl, aromatic ring or benzyl; n is 1 or 2; "" denotes the chiral center of the compound.
The photosensitizer is tetraphenylporphyrin:
the temperature of the asymmetric catalytic oxidation reaction is-40 to 100 ℃; the molar ratio of the chiral Salan-copper catalyst to the beta-keto ester compound is 0.001-2: 1; the molar ratio of the photosensitizer to the beta-keto ester compound is 0.01-0.1: 1; the visible light has a wavelength of 370-700 nm.
Further, the temperature of the asymmetric catalytic oxidation reaction is-40-25 ℃; the molar ratio of the chiral Salan-copper catalyst to the beta-keto ester compound is 0.05-0.2: 1; the molar ratio of the photosensitizer to the beta-keto ester compound is 0.05-0.1: 1.
The aromatic hydrocarbon solvent is toluene, xylene, o-xylene, m-xylene, p-xylene, 1,3, 5-trimethylbenzene, trifluoromethylbenzene, trichloromethylbenzene or tetrahydronaphthalene.
The invention has the beneficial effects that: the invention does not use any organic or inorganic oxidant, uses sustainable and environment-friendly air as the oxidant, uses inexhaustible visible light or sunlight as the light source, and uses the Salan-copper catalyst which is easy to synthesize, low in price and stable in property, can effectively prepare the chiral alpha-hydroxy-beta-keto ester compound, has high-efficiency conversion reaction, has the conversion rate of more than 80 percent, the stereoselectivity of more than 80 percent and the highest 96 percent ee, is simple to operate, has low cost and is suitable for industrialization.
Detailed Description
The following describes specific embodiments of the present invention in detail with reference to the technical solutions.
EXAMPLE 1 preparation of (2S) -5-chloro-2-hydroxy-1-oxo-2, 3-dihydro-1H-indene-2-carboxylic acid methyl ester (formula IV, where R is1，R3Is H, R2Is Cl, R4Is Me)
6,6' - (((1S,2S) -1,2-diphenylethane-1,2-diyl) bis (azanediyl) -bis (methyl)) bis (2, 4-di-tert-butyl lphenol) (formula II, 0.01428g, 0.022mmol) and copper triflate (0.00724g, 0.02mmol) were dissolved in 1mL of toluene. After stirring at 50 ℃ for 30 minutes, it was cooled at-15 ℃. After cooling, 5-chloro-2, 3-dihydro-1-oxo is added to the toluene solutionmethyl-1H-indene-2-carboxylate (formula III, wherein R is1，R3Is H, R2Is Cl, R4Me, 0.04496g, 0.2mmol) and tetraphenylporphyrin (0.00308g, 0.005mmol), the reaction was irradiated with a 5W visible LED lamp, and the toluene solution was allowed to contact with air, reacted for 15 hours, and then separated and purified by column chromatography. Methyl 5-chloro-2-hydroxy-1-oxo-2, 3-dihydro-1H-indene-2-carboxylate gave 94% yield with the ee value of the S-enantiomer being 96%.1H NMR(500MHz,Chloroform-d)δ7.73(d,J＝8.2Hz,1H),7.50(d,J＝1.6Hz,1H),7.42(dd,J＝8.2,1.6Hz,1H),3.96(s,1H),3.75(s,3H),3.70(d,J＝17.4Hz,1H),3.23(d,J＝17.4Hz,1H)。
EXAMPLE 2 preparation of (2S) -2-hydroxy-1-oxo-2, 3-dihydro-1H-indene-2-carboxylic acid methyl ester (formula IV, where R is1，R2，R3Is H, R4Is Me)
6,6' - (((1S,2S) -1,2-diphenylethane-1,2-diyl) bis (azanediyl) -bis (methyl)) bis (2, 4-di-tert-butyl lphenol) (formula II, 0.01428g, 0.022mmol) and copper triflate (0.00724g, 0.02mmol) were dissolved in 1mL of toluene. After stirring at 50 ℃ for 30 minutes, it was cooled at-15 ℃. After cooling, methyl 2, 3-dihydro-1-oxo-1H-indene-2-carboxylate (formula III, wherein R is1，R2，R3Is H, R4Me, 0.03802g, 0.2mmol) and tetraphenylporphyrin (0.00308g, 0.005mmol), the reaction was irradiated with a 5W visible LED lamp, and the toluene solution was allowed to contact with air, reacted for 15 hours, and then separated and purified by column chromatography. Methyl 2-hydroxy-1-oxo-2, 3-dihydro-1H-indene-2-carboxylate gave 89% yield with the ee value of the S-enantiomer being 89%.1H NMR(500MHz,Chloroform-d)δ7.81(d,J＝7.7Hz,1H),7.67(td,J＝7.7,1.2Hz,1H),7.50(dt,J＝7.7,1.2Hz,1H),7.47–7.40(m,1H),3.96(s,1H),3.74(s,3H),3.74(d,J＝17.3Hz,1H),3.26(d,J＝17.3Hz,1H)。
EXAMPLE 3 preparation of (2S) methyl 5-bromo-2-hydroxy-1-oxo-2, 3-dihydro-1H-indene-2-carboxylate (formula IV, where R is1，R3Is H, R2Is Br, R4Is Me)
6,6'-((((1S,2S)-1,2-diphenylethane-1,2-diyl)bis(azanediyl)) -bis (methyl) bis (2, 4-di-tert-butyl lphenol) (formula II, 0.01428g, 0.022mmol) and copper triflate (0.00724g, 0.02mmol) were dissolved in 1mL of toluene. After stirring at 50 ℃ for 30 minutes, it was cooled at-15 ℃. After cooling, 5-bromo-2, 3-dihydro-1-oxo-1H-indene-2-carboxylic acid methyl ester (formula III, wherein R is1，R3Is H, R2Is Br, R4Me, 0.05382g, 0.2mmol) and tetraphenylporphyrin (0.00308g, 0.005mmol), the reaction was irradiated with a 5W visible LED lamp, and the toluene solution was allowed to contact with air, reacted for 15 hours, and then separated and purified by column chromatography. 5-bromo-2-hydroxy-1-oxo-2, 3-dihydro-1H-indene-2-carboxylic acid methyl ester gave a 91% yield with an ee value of the S-enantiomer of 93%.1H NMR(500MHz,Chloroform-d)δ7.92(d,J＝1.9Hz,1H),7.77(dd,J＝8.1,1.9Hz,1H),7.39(d,J＝8.1,Hz,1H),3.95(s,1H),3.75(s,3H),3.67(d,J＝17.4Hz,1H),3.19(d,J＝17.4Hz,1H)。
EXAMPLE 4 preparation of (2S) methyl 4-bromo-2-hydroxy-1-oxo-2, 3-dihydro-1H-indene-2-carboxylate (formula IV, where R is2，R3Is H, R1Is Br, R4Is Me)
6,6' - (((1S,2S) -1,2-diphenylethane-1,2-diyl) bis (azanediyl) -bis (methyl)) bis (2, 4-di-tert-butyl lphenol) (formula II, 0.01428g, 0.022mmol) and copper triflate (0.00724g, 0.02mmol) were dissolved in 1mL of toluene. After stirring at 50 ℃ for 30 minutes, it was cooled at-15 ℃. After cooling, 4-bromo-2, 3-dihydro-1-oxo-1H-indene-2-carboxylic acid methyl ester (formula III, wherein R is2，R3Is H, R1Is Br, R4Me, 0.05382g, 0.2mmol) and tetraphenylporphyrin (0.00308g, 0.005mmol), the reaction was irradiated with a 5W visible LED lamp, and the toluene solution was allowed to contact with air, reacted for 15 hours, and then separated and purified by column chromatography. Methyl 4-bromo-2-hydroxy-1-oxo-2, 3-dihydro-1H-indene-2-carboxylate gave 87% yield with an ee value of 58% for the S-enantiomer.1H NMR(500MHz,Chloroform-d)δ7.84(dd,J＝7.8,1.0Hz,1H),7.76(dd,J＝7.8,1.0Hz,1H),7.35(dd,J＝7.8,1.0Hz,1H),4.00(s,1H),3.77(s,3H),3.68(d,J＝17.8Hz,1H),3.18(d,J＝17.8Hz,1H)。
EXAMPLE 5 preparation of (2S) methyl 6-bromo-2-hydroxy-1-oxo-2, 3-dihydro-1H-indene-2-carboxylate (formula IV, where R is1，R2Is H, R3Is Br, R4Is Me)
6,6' - (((1S,2S) -1,2-diphenylethane-1,2-diyl) bis (azanediyl) -bis (methyl)) bis (2, 4-di-tert-butyl lphenol) (formula II, 0.01428g, 0.022mmol) and copper triflate (0.00724g, 0.02mmol) were dissolved in 1mL of toluene. After stirring at 50 ℃ for 30 minutes, it was cooled at-15 ℃. After cooling, 6-bromo-2, 3-dihydro-1-oxo-1H-indene-2-carboxylic acid methyl ester (formula III, wherein R is1，R2Is H, R3Is Br, R4Me, 0.05382g, 0.2mmol) and tetraphenylporphyrin (0.00308g, 0.005mmol), the reaction was irradiated with a 5W visible LED lamp, and the toluene solution was allowed to contact with air, reacted for 15 hours, and then separated and purified by column chromatography. Methyl 6-bromo-2-hydroxy-1-oxo-2, 3-dihydro-1H-indene-2-carboxylate gave 85% yield with an ee of 84% for the S-enantiomer.1H NMR(500MHz,Chloroform-d)δ7.92(d,J＝2.0Hz,1H),7.77(dd,J＝8.2,2.0Hz,1H),7.39(d,J＝8.2Hz,1H),3.97(s,1H),3.75(s,3H),3.67(d,J＝17.4Hz,1H),3.19(d,J＝17.4Hz,1H)。
EXAMPLE 6 preparation of (2S) methyl 4-methoxy-2-hydroxy-1-oxo-2, 3-dihydro-1H-indene-2-carboxylate (formula IV, where R is2，R3Is H, R1Is OMe, R4Is Me)
6,6' - (((1S,2S) -1,2-diphenylethane-1,2-diyl) bis (azanediyl) -bis (methyl)) bis (2, 4-di-tert-butyl lphenol) (formula II, 0.01428g, 0.022mmol) and copper triflate (0.00724g, 0.02mmol) were dissolved in 1mL of toluene. After stirring at 50 ℃ for 30 minutes, it was cooled at-15 ℃. After cooling, 4-methoxy-2, 3-dihydro-1-oxo-1H-indene-2-carboxylic acid methyl ester (formula III, wherein R is2，R3Is H, R1Is OMe, R4Me, 0.04404g, 0.2mmol) and tetraphenylporphyrin (0.00308g, 0.005mmol), the reaction was irradiated with a 5W visible LED lamp, and the toluene solution was allowed to contact with air, reacted for 15 hours, and then separated and purified by column chromatography. 4-methoxy-2-hydroxy-1-oxo-2, 3-dihydroMethyl (E) -1H-indene-2-carboxylate gave a 91% yield with an ee of 96% for the S-enantiomer.1H NMR(500MHz,Chloroform-d)δ7.43–7.37(m,2H),7.11(dd,J＝6.9,1.9Hz,1H),3.93(s,1H),3.92(s,3H),3.74(s,3H),3.66(d,J＝17.7Hz,1H),3.11(d,J＝17.7Hz,1H)。
EXAMPLE 7 preparation of (2S) methyl 5-methoxy-2-hydroxy-1-oxo-2, 3-dihydro-1H-indene-2-carboxylate (formula IV, where R is1，R2Is H, R2Is OMe, R4Is Me)
6,6' - (((1S,2S) -1,2-diphenylethane-1,2-diyl) bis (azanediyl) -bis (methyl)) bis (2, 4-di-tert-butyl lphenol) (formula II, 0.01428g, 0.022mmol) and copper triflate (0.00724g, 0.02mmol) were dissolved in 1mL of toluene. After stirring at 50 ℃ for 30 minutes, it was cooled at-15 ℃. After cooling, methyl 5-methoxy-2, 3-dihydro-1-oxo-1H-indene-2-carboxylate (formula III, wherein R is2，R3Is H, R1Is OMe, R4Me, 0.04404g, 0.2mmol) and tetraphenylporphyrin (0.00308g, 0.005mmol), the reaction was irradiated with a 5W visible LED lamp, and the toluene solution was allowed to contact with air, reacted for 15 hours, and then separated and purified by column chromatography. 5-methoxy-2-hydroxy-1-oxo-2, 3-dihydro-1H-indene-2-carboxylic acid methyl ester gave a 91% yield with an ee value of the S-enantiomer of 96%.1H NMR(500MHz,Chloroform-d)δ7.74(d,J＝8.6Hz,1H),6.96(dd,J＝8.6,2.3Hz,1H),6.91(d,J＝2.3Hz,1H),3.92(s,3H),3.91(s,1H),3.74(s,3H),3.68(d,J＝17.2Hz,1H),3.20(d,J＝17.2Hz,1H)。
EXAMPLE 8 preparation of (2S) methyl 4-ethoxy-2-hydroxy-1-oxo-2, 3-dihydro-1H-indene-2-carboxylate (formula IV, where R is2，R3Is H, R1Is OEt, R4Is Me)
6,6' - (((1S,2S) -1,2-diphenylethane-1,2-diyl) bis (azanediyl) -bis (methyl)) bis (2, 4-di-tert-butyl lphenol) (formula II, 0.01428g, 0.022mmol) and copper triflate (0.00724g, 0.02mmol) were dissolved in 1mL of toluene. After stirring at 50 ℃ for 30 minutes, it was cooled at-15 ℃. After cooling, 4-ethoxy-2, 3-dihydro-1-oxo-1H-indene-2-carboxylic acid methyl ester (formula III, wherein R is2，R3Is H, R1Is OEt, R4Me, 0.04685g, 0.2mmol) and tetraphenylporphyrin (0.00308g, 0.005mmol), the reaction was irradiated with a 5W visible LED lamp, and the toluene solution was allowed to contact with air, reacted for 15 hours, and then separated and purified by column chromatography. Methyl 4-ethoxy-2-hydroxy-1-oxo-2, 3-dihydro-1H-indene-2-carboxylate gave a yield of 90% and the ee value of the S-enantiomer was 86%.1H NMR(500MHz,Chloroform-d)δ7.40–7.35(m,2H),7.09(dd,J＝5.6,3.3Hz,1H),4.13(q,J＝7.0Hz,1H),3.91(s,1H),3.74(s,3H),3.67(d,J＝17.7Hz,1H),3.12(d,J＝17.7Hz,1H),1.47(t,J＝7.0Hz,3H)。
EXAMPLE 9 preparation of (2S) ethyl 4-methoxy-2-hydroxy-1-oxo-2, 3-dihydro-1H-indene-2-carboxylate (formula IV, where R is2，R3Is H, R1Is OMe, R4To Et)
6,6' - (((1S,2S) -1,2-diphenylethane-1,2-diyl) bis (azanediyl) -bis (methyl)) bis (2, 4-di-tert-butyl lphenol) (formula II, 0.01428g, 0.022mmol) and copper triflate (0.00724g, 0.02mmol) were dissolved in 1mL of toluene. After stirring at 50 ℃ for 30 minutes, it was cooled at-15 ℃. After cooling, ethyl 4-methoxy-2, 3-dihydro-1-oxo-1H-indene-2-carboxylate (formula III, wherein R is2，R3Is H, R1Is OMe, R40.04685g, 0.2mmol) and tetraphenylporphyrin (0.00308g, 0.005mmol), the reaction system was irradiated with a 5W visible LED lamp and the toluene solution was allowed to contact air, reacted for 15 hours and then isolated and purified by column chromatography. Ethyl 4-methoxy-2-hydroxy-1-oxo-2, 3-dihydro-1H-indene-2-carboxylate gave 89% yield with an ee value of 90% for the S-enantiomer.1H NMR(500MHz,Chloroform-d)δ7.43–7.37(m,2H),7.11(dd,J＝6.7,2.1Hz,1H),4.22(qd,J＝7.1,3.2Hz,2H),3.96(s,1H),3.92(s,3H),3.64(d,J＝17.7Hz,1H),3.11(d,J＝17.7Hz,1H),1.19(t,J＝7.1Hz,2H)。
EXAMPLE 10 preparation of (2S) 4-methoxy-2-hydroxy-1-oxo-2, 3-dihydro-1H-indene-2-carboxylic acid isopropyl ester (formula IV, where R is2，R3Is H, R1Is OMe, R4Is iPr)
6,6'-((((1S,2S) -1,2-diphenylethane-1,2-diyl) bis (azanediyl) -bis (methylene) bis (2, 4-di-tert-butyl lphenol) (formula II, 0.01428g, 0.022mmol) and copper triflate (0.00724g, 0.02mmol) were dissolved in 1mL of toluene. After stirring at 50 ℃ for 30 minutes, it was cooled at-15 ℃. After cooling, 4-methoxy-2, 3-dihydro-1-oxo-1H-indene-2-carboxylic acid isopropyl ester (formula III, wherein R is2，R3Is H, R1Is OMe, R40.04965g, 0.2mmol) and tetraphenylporphyrin (0.00308g, 0.005mmol), the reaction system was irradiated with a 5W visible LED lamp and the toluene solution was allowed to contact air, reacted for 15 hours and then isolated and purified by column chromatography. 4-methoxy-2-hydroxy-1-oxo-2, 3-dihydro-1H-indene-2-carboxylic acid isopropyl ester gave a 90% yield with an ee value of the S-enantiomer of 93%.1H NMR(500MHz,Chloroform-d)δ7.43–7.36(m,2H),7.10(dd,J＝6.9,2.0Hz,1H),5.08(hept,J＝6.3Hz,1H),3.98(s,1H),3.92(s,3H),3.61(d,J＝17.6Hz,1H),3.10(d,J＝17.6Hz,1H),1.21(d,J＝6.3Hz,3H),1.14(d,J＝6.3Hz,3H)。
Claims (5)
1. A method for preparing chiral alpha-hydroxy-beta-keto ester compound by using visible light to initiate aerobic Salan-copper catalyst is characterized by comprising the following steps: in an aromatic hydrocarbon solvent, visible light irradiates a photosensitizer to excite oxygen to be singlet oxygen, the singlet oxygen attacks a beta-keto ester compound activated by a chiral Salan-copper catalyst to carry out asymmetric catalytic oxidation reaction, and an alpha-hydroxy-beta-keto ester compound with optical activity is prepared;
the chiral Salan-copper catalyst is a (1S,2S) -1, 2-diphenyldiamine derivative Salan-copper catalyst, and the structure of the catalyst is shown as a formula I:
wherein the complex is copper chloride, copper perchlorate, copper acetate, copper acetylacetonate or copper trifluoromethanesulfonate; the ligand is of formula II:
wherein, (1S,2S) -1, 2-diphenyldiamine is a connecting chain; r 'and R' are halogen, NO2Cyano, C2-C8Alkyl radical, C5-C6Cycloalkyl radical, C2-C8Alkoxy, adamantyl, benzene ring, five-membered aromatic heterocycle, six-membered aromatic heterocycle or 1-naphthyl, R 'and R' are the same or different;
the beta-ketoester compound is of formula III:
wherein R is1、R2And R3Is a hydrogen atom, halogen, alkyl or alkoxy, R1、R2And R3The same or different; r4Is alkyl, cycloalkyl, aromatic ring or benzyl; n is 1 or 2;
the photosensitizer is tetraphenylporphyrin, copper tetraphenylporphyrin, phthalocyanine, copper phthalocyanine, eosin E, eosin Y, rose bengal, acetophenone or benzophenone.
2. The method of claim 1, wherein the α -hydroxy- β -ketoester compound is of formula iv:
wherein R is1、R2And R3Is a hydrogen atom, halogen, alkyl or alkoxy, R1、R2And R3The same or different; r4Is alkyl, cycloalkyl, aromatic ring or benzyl; n is 1 or 2; "" denotes the chiral center of the compound.
3. The method according to claim 1 or 2, wherein the temperature of the asymmetric catalytic oxidation reaction is-40 to 100 ℃; the molar ratio of the chiral Salan-copper catalyst to the beta-keto ester compound is 0.001-2: 1; the molar ratio of the photosensitizer to the beta-keto ester compound is 0.01-0.1: 1; the visible light has a wavelength of 370-700 nm.
4. The method according to claim 1 or 2, wherein the aromatic hydrocarbon solvent is toluene, xylene, 1,3, 5-trimethylbenzene, trifluoromethylbenzene, trichloromethylbenzene or tetrahydronaphthalene.
5. The method according to claim 3, wherein the temperature of the asymmetric catalytic oxidation reaction is-40 to 25 ℃; the molar ratio of the chiral Salan-copper catalyst to the beta-keto ester compound is 0.05-0.2: 1; the molar ratio of the photosensitizer to the beta-keto ester compound is 0.05-0.1: 1.
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