CN108516937A - A kind of method that visible light-initiated aerobic Salan- copper catalysts prepare chiral alpha-hydroxy-beta -one ester compound - Google Patents

A kind of method that visible light-initiated aerobic Salan- copper catalysts prepare chiral alpha-hydroxy-beta -one ester compound Download PDF

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CN108516937A
CN108516937A CN201810466329.5A CN201810466329A CN108516937A CN 108516937 A CN108516937 A CN 108516937A CN 201810466329 A CN201810466329 A CN 201810466329A CN 108516937 A CN108516937 A CN 108516937A
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beta
salan
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copper
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CN108516937B (en
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孟庆伟
杨帆
赵静喃
刘广志
唐晓飞
武玉峰
尹航
冯世豪
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Dalian University of Technology
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
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    • C07B2200/07—Optical isomers
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane

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Abstract

The present invention provides a kind of method that visible light-initiated aerobic Salan copper catalysts prepare chiral alpha hydroxyl β keto ester compound by utilizing, belongs to photocatalysis asymmetric syntheses technical field.This method is in aromatic hydrocarbon solvent, it is active singlet oxygen that radiation of visible light photosensitizer, which excites oxygen, the β keto ester compound by utilizing that singlet oxygen attack is activated by chiral Salan copper catalysts carries out asymmetry catalysis oxidation reaction, and α hydroxyls β keto ester compound by utilizing with optical activation is prepared.Present invention uses the Salan copper catalysts being readily synthesized, price is low, property is stablized, and can effectively prepare chiral alpha hydroxyl β keto ester compound by utilizing, obtain very high yield and good enantioselectivity.

Description

The visible light-initiated aerobic Salan- copper catalysts of one kind preparing chiral alpha-hydroxy-beta -one The method of ester compound
Technical field
The invention belongs to photocatalysis asymmetric syntheses technical fields, using oxygen or air as oxidant or final oxygen atom Source is excited into the singlet oxygen with reactivity under visible light illumination, and (1S, 2S) -1,2- diphenyl diamines is utilized to spread out Biology is ligand, and the complex of metal is catalyst centered on copper trifluoromethanesulfcomposite, prepares chiral alpha-hydroxy-beta -one acid esters chemical combination The method of object.
Background technology
Some Alpha-hydroxy-beta-ketoester compounds with optical activation are important structural unit, widely exist in Natural products is used to prepare drug, pesticide and fine chemical product as intermediate.Prepare chiral alpha-hydroxy-beta -one acid esters chemical combination The catalysis oxidation beta-ketoester compounds that object is most ideal, simple, fast method is exactly enantioselectivity.Davis was in 1981 Method (the Tetrahedron that chiral ɑ-hydroxy-beta-dicarbonyl compound is obtained using Davis reagents is reported for the first time Lett.1981,22,4385-4388), but this method is cumbersome, reaction condition is more harsh, uses excessive chiral oxygen Agent, cost is higher, is not suitable for production application.
In recent years, researchers report a large amount of asymmetric syntheses chiral alpha-hydroxy-beta -one ester compound Method, including 1) organic catalysis；2) metal complex.For organic catalysis, patent WO 03/040083 and document J.Org.Chem.2004,69,8165-8167 to disclose with cinchona alkaloid and its derivative be organic catalyst, organic mistake Oxide is oxidant, prepares a kind of method of chiral alpha-hydroxy-beta-dicarbonyl compound, and wherein oxidation products yield is generally 80-90%, corresponding selection are generally 50-80%ee.The fragrant oxygen alkamine catalyst of inventor seminar independent development (Tetrahedron.2012,38,7973-7977), and Diterpenoid Alkaloids lappaconitine (Synlett.2009,16,2659- 2662) also there is preferable catalytic effect, however, these method reaction time are long, enantioselectivity is not very ideal.In addition golden In terms of metal complex, document (Proc.Natl.Acad.Sci.U.S.A.2004,101,5810-5814) reports winestone for the first time The metal complex of chiral ligand derived from acid and tetravalence Ti coordinations；In recent years Feng seminars report tartaric acid derivatives with The complex compound of Mg coordinations is catalyst (Adv.Synth.Catal.2013,355,1924-1930)；The salen ligands of Che reports The complex formed with Fe can also obtain some preferable knots for catalyst (Chem.Commun.2014,50,7870-7873) Fruit.But the oxidant of these methods application is generally complicated azepine oxirane.These factors limit above-mentioned The application of two class methods.For preparing chiral alpha-hydroxy-beta -one ester compound, it is still desirable to improve the system of more economical environmental protection Preparation Method.And in recent years, oxygen or air are developed as the method for oxidant or final oxygen atom source, especially Using visible-light activated oxygen to which catalysis oxidation organic reaction is even more to have obtained the attention of chemists.Inventor seminar is certainly Chem.Asian J.2012,7, main exploitation organic catalyst cinchona alkaloid-derived ligands and tetraphenylporphyrin photosensitizer synergistic effect are ( 2019-2023), Xiao Wen essences seminar utilizes Box-Ni catalyst and photosensitizer catalytic oxidation (J.Am.Chem.Soc.2017,139,63-66).However, these methods have limitation to the range of reactant, theirs are limited Extensive use.Therefore, the present invention provides the chiral Alpha-hydroxy-of a more sustainable preparation in terms of the energy and environmental protection The synthetic method of beta-ketoester compounds.
Invention content
The present invention is intended to provide a kind of using oxygen either air as oxidant or the visible light in final oxygen atom source It is catalyzed beta-ketoester compounds asymmetry 'alpha '-hydroxylation reaction method.Chirality (1S, 2S) -1,2- diphenyl diamine derivatives be with The copper complex of body (Salan) is catalyst, and photosensitizer tetraphenylporphyrin excitation oxygen is active list under visible light illumination Line state oxygen interacts with beta-ketoester compounds (III), carries out asymmetric 'alpha '-hydroxylation reaction, prepares Alpha-hydroxy-beta-ketoester The method of compound (IV).
Technical scheme of the present invention：
A kind of method that visible light-initiated aerobic Salan- copper catalysts prepare chiral alpha-hydroxy-beta -one ester compound, Steps are as follows：In aromatic hydrocarbon solvent, it is seen that it is singlet oxygen that irradiation sensitising agent, which excites oxygen, and singlet oxygen attack is chiral The beta-ketoester compounds of Salan- copper catalysts activation carry out asymmetry catalysis oxidation reaction, are prepared with optical activity Alpha-hydroxy-beta-ketoester compounds.
The chiral Salan- copper catalysts are (1S, 2S) -1,2- diphenyl diamine derivative Salan- copper catalysts, Structure such as Formulas I：
Wherein, complex is copper chloride, cupric perchlorate, copper acetate, acetylacetone copper or copper trifluoromethanesulfcomposite；Ligand such as formula II：
Wherein, (1S, 2S) -1,2- diphenyl diamines are connection chain；R ' and R " is halogen, NO2, cyano, C2-C8Alkyl, C5-C6Naphthenic base, C2-C8Alkoxy, adamantyl, phenyl ring base, five yuan of heteroaromatics, hexa-atomic heteroaromatic or 1- naphthalenes, R ' and R " phases It is same or different.
The photosensitizer is tetraphenylporphyrin, tetraphenylporphyrin copper, phthalocyanine, CuPc, eosin E, eosin Y, Bangladesh's rose Rare red, acetophenone or benzophenone.
The beta-ketoester compounds such as formula III：
Wherein, R1、R2And R3For hydrogen atom, halogen, alkyl or alkoxy, R1、R2And R3It is identical or different；R4For alkyl, Naphthenic base, aromatic ring or benzyl；N takes 1 or 2.
Alpha-hydroxy-the beta-ketoester compounds such as formula IV：
Wherein, R1、R2And R3For hydrogen atom, halogen, alkyl or alkoxy, R1、R2And R3It is identical or different；R4For alkyl, Naphthenic base, aromatic ring or benzyl；N takes 1 or 2；" * " indicates the chiral centre of compound.
The photosensitizer is tetraphenylporphyrin：
The temperature of the asymmetry catalysis oxidation reaction is -40~100 DEG C；Chiral Salan- copper catalysts and beta-ketoester The molar ratio of compound is 0.001~2:1；The molar ratio of photosensitizer and beta-ketoester compounds is 0.01~0.1:1；Visible light It is 370~700nm for wavelength.
Further, the temperature of the asymmetry catalysis oxidation reaction is -40~25 DEG C；Chiral Salan- copper catalysts with The molar ratio of beta-ketoester compounds is 0.05~0.2:1；The molar ratio of photosensitizer and beta-ketoester compounds is 0.05~ 0.1:1。
The aromatic hydrocarbon solvent is toluene, dimethylbenzene, ortho-xylene, meta-xylene, paraxylene, 1,3,5- front threes Benzene, trifluoromethylbenzene, benzenyl trichloride or naphthane.
Beneficial effects of the present invention：The present invention does not have to any organic and inorganic oxidant, has used sustainable, environmental-friendly Air as oxidant, inexhaustible visible light or sunlight as light source, and be readily synthesized, price is low, property Stable Salan- copper catalysts can effectively prepare chiral alpha-hydroxy-beta -one ester compound, react Efficient Conversion, conversion Rate is up to 80% or more, and stereoselectivity is higher than 80%, highest 96%ee, easy to operate, at low cost, suitable industrialization.
Specific implementation mode
Specific embodiments of the present invention are described in detail with reference to technical solution.
Preparation (2S) -5- chlorine-2-hydroxyl -1- oxo -2, the 3- dihydro -1H- indenes -2- of embodiment 1 carboxylate methyl esters (formula IV, Middle R1, R3For H, R2For Cl, R4For Me)
6,6'-((((1S,2S)-1,2-diphenylethane-1,2-diyl)bis(azanediyl))-bis (methylene)) bis (2,4-di-tert-buty lphenol) (Formula II, 0.01428g, 0.022mmol) and trifluoro methylsulphur Sour copper (0.00724g, 0.02mmol) is dissolved in 1mL toluene.After being stirred 30 minutes at 50 DEG C, puts it into -15 DEG C and drop Temperature.Be added in this backward toluene solution of cooling 5- chloro- 2,3- dihydros -1- oxos -1H- indenes -2- carboxylate methyl esters (formula III, wherein R1, R3For H, R2For Cl, R4For Me, 0.04496g, 0.2mmol) and tetraphenylporphyrin (0.00308g, 0.005mmol), use 5W Visible LED light irradiation reaction system, and this toluene solution is made to be contacted with air, column chromatographic isolation and purification after reaction 15 hours. 5- chlorine-2-hydroxyl -1- oxo -2,3- dihydro -1H- indenes -2- carboxylate methyl esters obtain 94% yield, and the ee values of S- enantiomters It is 96%.1H NMR (500MHz, Chloroform-d) δ 7.73 (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).
Embodiment 2 prepares (2S) -2- hydroxyl -1- oxo -2,3- dihydro -1H- indenes -2- carboxylate methyl ester (formula IV, wherein R1, R2, R3For H, R4For Me)
6,6'-((((1S,2S)-1,2-diphenylethane-1,2-diyl)bis(azanediyl))-bis (methylene)) bis (2,4-di-tert-buty lphenol) (Formula II, 0.01428g, 0.022mmol) and trifluoro methylsulphur Sour copper (0.00724g, 0.02mmol) is dissolved in 1mL toluene.After being stirred 30 minutes at 50 DEG C, puts it into -15 DEG C and drop Temperature.2,3- dihydro -1- oxo -1H- indenes -2- carboxylate methyl ester (formula III, wherein R are added in this backward toluene solution of cooling1, R2, R3For H, R4For Me, 0.03802g, 0.2mmol) and tetraphenylporphyrin (0.00308g, 0.005mmol), with 5W visible LED lamps Reaction system is irradiated, and this toluene solution is made to be contacted with air, column chromatographic isolation and purification after reaction 15 hours.2- hydroxyl -1- oxygen Generation -2,3- dihydro -1H- indenes -2- carboxylate methyl esters obtain 89% yield, and the ee values of S- enantiomters are 89%.1H NMR (500MHz, Chloroform-d) δ 7.81 (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).
Bromo- 2- hydroxyls -1- oxos -2, the 3- dihydro -1H- indenes -2- carboxylate methyl esters of preparation (2S) 5- of embodiment 3 (formula IV, wherein Wherein R1, R3For H, R2For Br, R4For Me)
6,6'-((((1S,2S)-1,2-diphenylethane-1,2-diyl)bis(azanediyl))-bis (methylene)) bis (2,4-di-tert-buty lphenol) (Formula II, 0.01428g, 0.022mmol) and trifluoro methylsulphur Sour copper (0.00724g, 0.02mmol) is dissolved in 1mL toluene.After being stirred 30 minutes at 50 DEG C, puts it into -15 DEG C and drop Temperature.Be added in this backward toluene solution of cooling 5- bromo- 2,3- dihydros -1- oxos -1H- indenes -2- carboxylate methyl esters (formula III, wherein R1, R3For H, R2For Br, R4For Me, 0.05382g, 0.2mmol) and tetraphenylporphyrin (0.00308g, 0.005mmol), use 5W Visible LED light irradiation reaction system, and this toluene solution is made to be contacted with air, column chromatographic isolation and purification after reaction 15 hours. Bromo- 2- hydroxyls -1- oxos -2, the 3- dihydro -1H- indenes -2- carboxylate methyl esters of 5- obtain 91% yield, and the ee values of S- enantiomters It is 93%.1H NMR (500MHz, Chloroform-d) δ 7.92 (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).
Bromo- 2- hydroxyls -1- oxos -2, the 3- dihydro -1H- indenes -2- carboxylate methyl esters of preparation (2S) 4- of embodiment 4 (formula IV, wherein R2, R3For H, R1For Br, R4For Me)
6,6'-((((1S,2S)-1,2-diphenylethane-1,2-diyl)bis(azanediyl))-bis (methylene)) bis (2,4-di-tert-buty lphenol) (Formula II, 0.01428g, 0.022mmol) and trifluoro methylsulphur Sour copper (0.00724g, 0.02mmol) is dissolved in 1mL toluene.After being stirred 30 minutes at 50 DEG C, puts it into -15 DEG C and drop Temperature.Be added in this backward toluene solution of cooling 4- bromo- 2,3- dihydros -1- oxos -1H- indenes -2- carboxylate methyl esters (formula III, wherein R2, R3For H, R1For Br, R4For Me, 0.05382g, 0.2mmol) and tetraphenylporphyrin (0.00308g, 0.005mmol), use 5W Visible LED light irradiation reaction system, and this toluene solution is made to be contacted with air, column chromatographic isolation and purification after reaction 15 hours. Bromo- 2- hydroxyls -1- oxos -2, the 3- dihydro -1H- indenes -2- carboxylate methyl esters of 4- obtain 87% yield, and the ee values of S- enantiomters It is 58%.1H NMR (500MHz, Chloroform-d) δ 7.84 (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).
Bromo- 2- hydroxyls -1- oxos -2, the 3- dihydro -1H- indenes -2- carboxylate methyl esters of preparation (2S) 6- of embodiment 5 (formula IV, wherein R1, R2For H, R3For Br, R4For Me)
6,6'-((((1S,2S)-1,2-diphenylethane-1,2-diyl)bis(azanediyl))-bis (methylene)) bis (2,4-di-tert-buty lphenol) (Formula II, 0.01428g, 0.022mmol) and trifluoro methylsulphur Sour copper (0.00724g, 0.02mmol) is dissolved in 1mL toluene.After being stirred 30 minutes at 50 DEG C, puts it into -15 DEG C and drop Temperature.Be added in this backward toluene solution of cooling 6- bromo- 2,3- dihydros -1- oxos -1H- indenes -2- carboxylate methyl esters (formula III, wherein R1, R2For H, R3For Br, R4For Me, 0.05382g, 0.2mmol) and tetraphenylporphyrin (0.00308g, 0.005mmol), use 5W Visible LED light irradiation reaction system, and this toluene solution is made to be contacted with air, column chromatographic isolation and purification after reaction 15 hours. Bromo- 2- hydroxyls -1- oxos -2, the 3- dihydro -1H- indenes -2- carboxylate methyl esters of 6- obtain 85% yield, and the ee values of S- enantiomters It is 84%.1H NMR (500MHz, Chloroform-d) δ 7.92 (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)。
Preparation (2S) 4- methoxyl group -2- hydroxyl -1- oxo -2, the 3- dihydro -1H- indenes -2- of embodiment 6 carboxylate methyl esters (formula IV, Wherein R2, R3For H, R1For OMe, R4For Me)
6,6'-((((1S,2S)-1,2-diphenylethane-1,2-diyl)bis(azanediyl))-bis (methylene)) bis (2,4-di-tert-buty lphenol) (Formula II, 0.01428g, 0.022mmol) and trifluoro methylsulphur Sour copper (0.00724g, 0.02mmol) is dissolved in 1mL toluene.After being stirred 30 minutes at 50 DEG C, puts it into -15 DEG C and drop Temperature.Be added in this backward toluene solution of cooling 4- methoxyl group -2,3- dihydro -1- oxo -1H- indenes -2- carboxylate methyl esters (formula III, Wherein R2, R3For H, R1For OMe, R4For Me, 0.04404g, 0.2mmol) and tetraphenylporphyrin (0.00308g, 0.005mmol), With 5W visible LED light irradiation reaction systems, and this toluene solution is made to be contacted with air, column chromatography for separation is pure after reaction 15 hours Change.4- methoxyl group -2- hydroxyl -1- oxo -2,3- dihydro -1H- indenes -2- carboxylate methyl esters obtain 91% yield, and S- enantiomerisms The ee values of body are 96%.1H NMR (500MHz, Chloroform-d) δ 7.43-7.37 (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)。
Preparation (2S) 5- methoxyl group -2- hydroxyl -1- oxo -2, the 3- dihydro -1H- indenes -2- of embodiment 7 carboxylate methyl esters (formula IV, Wherein R1, R2For H, R2For OMe, R4For Me)
6,6'-((((1S,2S)-1,2-diphenylethane-1,2-diyl)bis(azanediyl))-bis (methylene)) bis (2,4-di-tert-buty lphenol) (Formula II, 0.01428g, 0.022mmol) and trifluoro methylsulphur Sour copper (0.00724g, 0.02mmol) is dissolved in 1mL toluene.After being stirred 30 minutes at 50 DEG C, puts it into -15 DEG C and drop Temperature.Be added in this backward toluene solution of cooling 5- methoxyl group -2,3- dihydro -1- oxo -1H- indenes -2- carboxylate methyl esters (formula III, Wherein R2, R3For H, R1For OMe, R4For Me, 0.04404g, 0.2mmol) and tetraphenylporphyrin (0.00308g, 0.005mmol), With 5W visible LED light irradiation reaction systems, and this toluene solution is made to be contacted with air, column chromatography for separation is pure after reaction 15 hours Change.5- methoxyl group -2- hydroxyl -1- oxo -2,3- dihydro -1H- indenes -2- carboxylate methyl esters obtain 91% yield, and S- enantiomerisms The ee values of body are 96%.1H NMR (500MHz, Chloroform-d) δ 7.74 (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).
Preparation (2S) 4- ethyoxyl -2- hydroxyl -1- oxo -2, the 3- dihydro -1H- indenes -2- of embodiment 8 carboxylate methyl esters (formula IV, Wherein R2, R3For H, R1For OEt, R4For Me)
6,6'-((((1S,2S)-1,2-diphenylethane-1,2-diyl)bis(azanediyl))-bis (methylene)) bis (2,4-di-tert-buty lphenol) (Formula II, 0.01428g, 0.022mmol) and trifluoro methylsulphur Sour copper (0.00724g, 0.02mmol) is dissolved in 1mL toluene.After being stirred 30 minutes at 50 DEG C, puts it into -15 DEG C and drop Temperature.Be added in this backward toluene solution of cooling 4- ethyoxyl -2,3- dihydro -1- oxo -1H- indenes -2- carboxylate methyl esters (formula III, Wherein R2, R3For H, R1For OEt, R4For Me, 0.04685g, 0.2mmol) and tetraphenylporphyrin (0.00308g, 0.005mmol), With 5W visible LED light irradiation reaction systems, and this toluene solution is made to be contacted with air, column chromatography for separation is pure after reaction 15 hours Change.4- ethyoxyl -2- hydroxyl -1- oxo -2,3- dihydro -1H- indenes -2- carboxylate methyl esters obtain 90% yield, and S- enantiomerisms The ee values of body are 86%.1H NMR (500MHz, Chloroform-d) δ 7.40-7.35 (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).
Preparation (2S) 4- methoxyl group -2- hydroxyl -1- oxo -2, the 3- dihydro -1H- indenes -2- of embodiment 9 carboxylic acid, ethyl esters (formula IV, Wherein R2, R3For H, R1For OMe, R4For Et)
6,6'-((((1S,2S)-1,2-diphenylethane-1,2-diyl)bis(azanediyl))-bis (methylene)) bis (2,4-di-tert-buty lphenol) (Formula II, 0.01428g, 0.022mmol) and trifluoro methylsulphur Sour copper (0.00724g, 0.02mmol) is dissolved in 1mL toluene.After being stirred 30 minutes at 50 DEG C, puts it into -15 DEG C and drop Temperature.Be added in this backward toluene solution of cooling 4- methoxyl group -2,3- dihydro -1- oxo -1H- indenes -2- carboxylic acid, ethyl esters (formula III, Wherein R2, R3For H, R1For OMe, R4For ethyl ester, 0.04685g, 0.2mmol) and tetraphenylporphyrin (0.00308g, 0.005mmol), with 5W visible LED light irradiation reaction systems, and this toluene solution is made to be contacted with air, after reaction 15 hours Column chromatographic isolation and purification.4- methoxyl group -2- hydroxyl -1- oxo -2,3- dihydro -1H- indenes -2- carboxylate methyl ester ethyl esters obtain 89% receipts Rate, and the ee values of S- enantiomters are 90%.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).
Embodiment 10 prepares (2S) 4- methoxyl group -2- hydroxyl -1- oxo -2,3- dihydro -1H- indenes -2- carboxylic acid isopropyl's (formulas IV, wherein R2, R3For H, R1For OMe, R4For iPr)
6,6'-((((1S,2S)-1,2-diphenylethane-1,2-diyl)bis(azanediyl))-bis (methylene)) bis (2,4-di-tert-buty lphenol) (Formula II, 0.01428g, 0.022mmol) and trifluoro methylsulphur Sour copper (0.00724g, 0.02mmol) is dissolved in 1mL toluene.After being stirred 30 minutes at 50 DEG C, puts it into -15 DEG C and drop Temperature.4- methoxyl group -2,3- dihydro -1- oxo -1H- indenes -2- carboxylic acid isopropyl's (formulas are added in this backward toluene solution of cooling III, wherein R2, R3For H, R1For OMe, R4For iPr, 0.04965g, 0.2mmol) and tetraphenylporphyrin (0.00308g, 0.005mmol), with 5W visible LED light irradiation reaction systems, and this toluene solution is made to be contacted with air, after reaction 15 hours Column chromatographic isolation and purification.4- methoxyl group -2- hydroxyl -1- oxo -2,3- dihydro -1H- indenes -2- carboxylic acid isopropyls obtain 90% receipts Rate, and the ee values of S- enantiomters are 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 (10)

1. a kind of method that visible light-initiated aerobic Salan- copper catalysts prepare chiral alpha-hydroxy-beta -one ester compound, It is characterized in that, steps are as follows：In aromatic hydrocarbon solvent, it is seen that it is singlet oxygen, singlet oxygen that irradiation sensitising agent, which excites oxygen, The beta-ketoester compounds that attack is activated by chiral Salan- copper catalysts carry out asymmetry catalysis oxidation reaction, and tool is prepared There are optically active Alpha-hydroxy-beta-ketoester compounds.
2. according to the method described in claim 1, it is characterized in that, the chiral Salan- copper catalysts be (1S, 2S) -1, 2- diphenyl diamine derivative Salan- copper catalysts, structure such as Formulas I：
Wherein, complex is copper chloride, cupric perchlorate, copper acetate, acetylacetone copper or copper trifluoromethanesulfcomposite；Ligand such as Formula II：
Wherein, (1S, 2S) -1,2- diphenyl diamines are connection chain；R ' and R " is halogen, NO2, cyano, C2-C8Alkyl, C5-C6Ring Alkyl, C2-C8Alkoxy, adamantyl, phenyl ring base, five yuan of heteroaromatics, hexa-atomic heteroaromatic or 1- naphthalenes, R ' and R " are identical or not Together.
3. method according to claim 1 or 2, which is characterized in that the photosensitizer is tetraphenylporphyrin, tetraphenylporphyrin Copper, phthalocyanine, CuPc, eosin E, eosin Y, Bengal rose red, acetophenone or benzophenone.
4. method according to claim 1 or 2, which is characterized in that the beta-ketoester compounds such as formula III：
Wherein, R1、R2And R3For hydrogen atom, halogen, alkyl or alkoxy, R1、R2And R3It is identical or different；R4For alkyl, cycloalkanes Base, aromatic ring or benzyl；N takes 1 or 2；
Alpha-hydroxy-the beta-ketoester compounds such as formula IV：
Wherein, R1、R2And R3For hydrogen atom, halogen, alkyl or alkoxy, R1、R2And R3It is identical or different；R4For alkyl, cycloalkanes Base, aromatic ring or benzyl；N takes 1 or 2；" * " indicates the chiral centre of compound.
5. according to the method described in claim 3, it is characterized in that, the beta-ketoester compounds such as formula III：
Wherein, R1、R2And R3For hydrogen atom, halogen, alkyl or alkoxy, R1、R2And R3It is identical or different；R4For alkyl, cycloalkanes Base, aromatic ring or benzyl；N takes 1 or 2；
Alpha-hydroxy-the beta-ketoester compounds such as formula IV：
Wherein, R1、R2And R3For hydrogen atom, halogen, alkyl or alkoxy, R1、R2And R3It is identical or different；R4For alkyl, cycloalkanes Base, aromatic ring or benzyl；N takes 1 or 2；" * " indicates the chiral centre of compound.
6. according to the method described in claim 1,2 or 5, which is characterized in that the temperature of the asymmetry catalysis oxidation reaction be- 40~100 DEG C；The molar ratio of chiral Salan- copper catalysts and beta-ketoester compounds is 0.001~2:1；Photosensitizer and β -one The molar ratio of ester compound is 0.01~0.1:1；Visible light is that wavelength is 370~700nm.
7. according to the method described in claim 3, it is characterized in that, the temperature of the asymmetry catalysis oxidation reaction be -40~ 100℃；The molar ratio of chiral Salan- copper catalysts and beta-ketoester compounds is 0.001~2:1；Photosensitizer and beta-ketoester The molar ratio of compound is 0.01~0.1:1；Visible light is that wavelength is 370~700nm.
8. according to the method described in claim 4, it is characterized in that, the temperature of the asymmetry catalysis oxidation reaction be -40~ 100℃；The molar ratio of chiral Salan- copper catalysts and beta-ketoester compounds is 0.001~2:1；Photosensitizer and beta-ketoester The molar ratio of compound is 0.01~0.1:1；Visible light is that wavelength is 370~700nm.
9. according to the method described in claim 1,2,5,7 or 8, which is characterized in that the aromatic hydrocarbon solvent is toluene, diformazan Benzene, ortho-xylene, meta-xylene, paraxylene, 1,3,5- trimethylbenzenes, trifluoromethylbenzene, benzenyl trichloride or naphthane.
10. according to the method described in claim 6, it is characterized in that, the temperature of the asymmetry catalysis oxidation reaction be -40~ 25℃；The molar ratio of chiral Salan- copper catalysts and beta-ketoester compounds is 0.05~0.2：1；Photosensitizer and beta-ketoester The molar ratio of compound is 0.05~0.1:1.
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