CN106748690B - Method for synthesizing ketone by catalyzing alkylene oxide with iron - Google Patents

Method for synthesizing ketone by catalyzing alkylene oxide with iron Download PDF

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CN106748690B
CN106748690B CN201611146873.9A CN201611146873A CN106748690B CN 106748690 B CN106748690 B CN 106748690B CN 201611146873 A CN201611146873 A CN 201611146873A CN 106748690 B CN106748690 B CN 106748690B
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iron
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CN106748690A (en
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韩维
刘彬彬
金凤莉
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Nanjing Normal University
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Abstract

The invention discloses a method for synthesizing ketone by catalyzing alkylene oxide with iron, belonging to the field of catalytic synthesis technology and fine chemical synthesis. The method is characterized in that under the promoting action of hydrosilane, air or oxygen is used as an oxidant, and alkene is catalyzed and oxidized by iron to synthesize the ketone compound. The method has the advantages of wide catalyst source, low cost and environmental protection; the oxidant is wide in source, cheap and does not generate waste; the reaction condition is mild, the selectivity is high and the yield is high; the substrate is wide and stable in source; the compatibility of the substrate functional group is good and the application range of the substrate is wide; complex alkene molecules are well converted to ketones. Under the optimized reaction conditions, the separation yield of the target product is as high as 98%.

Description

Method for synthesizing ketone by catalyzing alkylene oxide with iron
Technical Field
The invention belongs to the field of catalytic synthesis technology and fine chemical synthesis, and particularly relates to an iron catalysis method for oxidation of complex alkene into ketone, which is a method for preparing ketone by oxidation of alkene with air or oxygen under iron catalysis.
Background
Structural units of ketones are widely present in organic compounds, and at the same time, it is a very important functional group for transformation, and is used for synthesis of medicines, pesticides, natural products, organic materials, and the like. Therefore, the universal, efficient, safe and economic method for synthesizing the ketone has important research significance and application value. The best known method for synthesizing ketone is Wacker oxidation reaction, which requires palladium as a catalyst, copper salt as an oxidation promoter and air as an oxidant, and the reaction can be smoothly carried out (b.w. michel, l.d. steffens, m.s. sigman, org.fact, 2014,84, 2.). Recently, Grubbs group reported a general method for preparing copper by oxidation of alkenes with palladium (5 mol%) and good catalytic effect was achieved at room temperature (US9096519B 2). However, the reaction still needs a noble metal palladium catalyst and benzoquinone as an oxidant or a pro-oxidant, and the large-scale industrial application of the method is severely limited. Iron has the advantages of large natural abundance, low price and low toxicity, and is an ideal catalyst metal. The development of iron-catalyzed processes has been a hotspot and difficulty of research. Iron-catalyzed oxidative studies of alkenes have predominantly been carried out in several reactions of epoxidation, dihydroxylation, anti-Markovnikov oxidation to aldehydes and oxidative cleavage of carbon-carbon double bonds (Miquel Costas, Giorgio Olivo, Olaf Cusso, chem. Asian J.,2016, DOI: 10.1002/asia.201601170). So far, effective iron-catalyzed reaction for synthesizing ketone from alkylene oxide has not been reported.
Disclosure of Invention
The technical problem to be solved is as follows: the invention aims to solve the technical problems that the existing Wacker oxidation reaction needs expensive palladium catalyst and copper as pro-oxidant, so that the reaction cost is high, and the removal of residual palladium in the pharmaceutical industry is difficult, and provides a method for synthesizing ketone by catalyzing alkylene oxide with iron, which has the characteristics of wide catalyst source, low cost and environmental protection; the oxidant is cheap and does not generate any waste; the substrate is wide and stable in source; the reaction condition is mild, the selectivity is good and the yield is high; the compatibility of substrate functional groups is good; the complex alkene molecule can efficiently synthesize the corresponding ketone.
The technical scheme is as follows: a method for synthesizing ketone by catalyzing alkylene oxide with iron specifically comprises the steps of preparing ketone by using hydrosilane as an additive, air or oxygen as an oxidant and iron as a catalyst in an organic solvent, water or an aqueous solution of the organic solvent, and oxidizing the alkylene oxide at the temperature of 20-180 ℃ for 0.25-60 hours;
the general reaction formula is shown as follows:
Figure BDA0001179079100000021
in the formula: r' represents aryl, heteroaryl, hydrogen, C1-C20 alkyl, C1-C20 halogen substituted alkyl, C3-C20 cycloalkyl, steroid alcohol group, sugar group or nucleoside group,
r' represents hydrogen, C1-C20 alkyl, C1-C20 halogen substituted alkyl, C3-C20 cycloalkyl, fluorine, chlorine, bromine, iodine, hydroxyl, C1-C20 alkylcarbonyl, C1-C20 alkoxycarbonyl, C1-C20 alkylaminocarbonyl, arylcarbonyl, heteroarylcarbonyl or C1-C20 alkylsulfonyl;
wherein, the aryl is substituted or unsubstituted phenyl, biphenyl, naphthyl, anthryl, phenanthryl or pyrenyl;
heteroaryl is a heteroaryl group containing a five to thirteen membered ring of N, O or S.
Further, the heteroaryl group is furyl, benzofuryl, thienyl, pyrrolyl, indolyl, carbazolyl, pyridyl, isoxazolyl, pyrazolyl, imidazolyl, oxazolyl, or thiazolyl.
Further, when R 'or R' is heteroaryl pyrrolyl, indolyl, carbazolyl, pyrazolyl or imidazolyl, the substituent on the nitrogen atom is selected from hydrogen, C1-C20 alkyl, C1-C20 halogen substituted alkyl, C3-C20 cycloalkyl, aryl, heteroaryl, C1-C20 alkylsulfonyl, p-toluenesulfonyl, benzyl, C1-C20 alkylcarbonyl, tert-butoxy acyl or aroyl.
Further, with R1Represents a substituent on the aryl group of R', R1Mono-or polysubstituted hydrogen on aromatic rings, R1Selected from hydrogen, C1-C20 alkyl, alkynyl, C1-C20 alkoxy, C1-C20 halogen substituted alkyl, C3-C20 cycloalkyl, aryl or aryloxy, heteroaryl, heteroaryloxy or heteroarylamino, arylcarbonyl, heteroarylcarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, C1-C20 mercapto, fluorine, chlorine or bromine, hydroxyl, C1-C20 alkylcarbonyl, carboxyl, C1-C20 alkoxycarbonyl, C1-C20 alkylaminocarbonyl, arylcarbonyl, C1-C20 alkylsulfonyl, sulfonic acid group and (B OH)2Cyano or nitro;
with R2Represents a substituent on R', R2Mono-or polysubstituted hydrogen on aromatic rings, R2Selected from hydrogen, C1-C20 alkyl, alkynyl, C1-C20 alkoxy, C1-C20 halogen substituted alkyl, C3-C20 cycloalkyl, aryl or aryloxy, heteroaryl, heteroaryloxy or heteroarylamino, arylcarbonyl, heteroarylcarbonyl, aryloxyCarbonyl, heteroaryloxycarbonyl, C1-C20 mercapto, fluorine, chlorine or bromine, hydroxyl, C1-C20 alkylcarbonyl, carboxyl, C1-C20 alkoxycarbonyl, C1-C20 alkylaminocarbonyl, arylcarbonyl, C1-C20 alkylsulfonyl, sulfonic acid, cyano or nitro.
Further, the iron is selected from iron powder, ferrous trifluoromethanesulfonate, ferric trifluoromethanesulfonate, ferrous chloride, ferrous acetylacetonate, ferric acetylacetonate, ferrous 2,2,6, 6-tetramethyl-3, 5-heptanedionate, ferrous 1, 3-diphenylpropanedionate, ferric 1, 3-diphenylpropanedionate, ferrous benzoylacetonate, ferric benzoylacetonate, ferrous ferricyanide, ferric ferricyanide, ferrous acetate, ferrous sulfate, ferrous ammonium sulfate, ferric sulfate, ferrous oxalate, ferric oxalate, ferrous fluoride, ferric fluoride, ferrous bromide, ferric iodide, ferric trichloride, ferric oxide, or ferroferric oxide.
Further, the hydrosilane is selected from the group consisting of trimethoxysilane, dimethylethoxysilane, triethylsilane, dimethylethylsilane, benzyldimethylsilane, triisopropylsilane, diethylsilane, dichlorosilanesdimethylmonochlorosilane, diisopropylchlorosilane, chloromethyl (dimethyl) silane, di-t-butylchlorosilane, diphenylchlorosilane, ethyldichlorosilane, di-t-butylsilane, methyldiphenylsilane, methyldichlorosilane, phenylsilane, diphenylsilane, triethoxysilane, t-butyldimethylsilane, dimethylphenylsilane, 1, 4-bis (dimethylsilyl) benzene, isopropoxyphenylsilane, methyldiethoxysilane, dimethoxy (methyl) silane, dimethylmethylhydrogen (siloxanes and polysiloxanes), 1,3, 3-tetraisopropyldisiloxane, dimethyldichlorosilane, 1,3, 3-dimethyldichlorosilane, and dimethyldichlorosilane, Tris (trimethylsilyl) silane, polymethylhydrosiloxane, methylphenylsilicone oil, 1,3, 3-tetramethyldisiloxane, pentamethyldisiloxane, tetrakis (dimethylsilyl) silane, 1, 3-bis (3,3, 3-trifluoropropyl) -1,1,3, 3-tetramethyldisiloxane, tetrakis (dimethylsiloxy) silane, phenyltris (dimethylsiloxy) silane or 1,1,2, 2-tetraphenyldisilane.
Further, the organic solvent is selected from methanol, ethanol, ethylene glycol, N-propanol, isopropanol, 1, 3-propanediol, glycerol, N-butanol, isobutanol, t-butanol, trifluoroethanol, 2-methyl-2-butanol, 3-methoxybutanol, sec-butanol, t-amyl alcohol, 4-methyl-2-pentanol, isoamyl alcohol, 2-pentanol, 3-pentanol, cyclopentanol, N-pentanol, polyethylene glycol 200-10000, acetonitrile, benzonitrile, toluene, dichloromethane, 1, 2-dichloroethane, dimethyl sulfoxide, N-dimethylformamide, N-diethylamide, ethyl acetate, 1, 4-dioxane or tetrahydrofuran.
Furthermore, the volume ratio of the organic solvent to water in the aqueous solution of the organic solvent is 1: 1-100.
Further, the gas pressure of the air or the oxygen is 1-10 atm.
Furthermore, the mol ratio of the alkene, the hydrosilane and the iron catalyst is 1 (0.5-50) to 0.001-10; the weight ratio of the alkene to the solvent is 1 (5-1000).
Has the advantages that:
(1) the invention provides a new method for preparing ketone by catalyzing air or oxygen alkylene oxide with iron promoted by hydrosilane, which has the unique advantages of cheap catalyst, promoter and oxidant, wide sources and environmental protection; the reaction condition is mild, the selectivity is high and the yield is high; the substrate has wide source, stability and easy processing; the compatibility of the substrate functional group is good and the application range of the substrate is wide; the reaction is suitable for the advantage of complex alkene molecular oxidation;
(2) the ketone synthesis method provided by the invention is simple, feasible and safe, the ketone can be directly obtained by one-step method, under the optimized reaction condition, the yield of the separated target product is up to 98%, and the method is a universal, efficient, economic and environment-friendly ketone synthesis method;
(3) the method of the invention can use ideal iron as a catalyst for reaction, and the key point is that hydrosilane is used as an accelerant, the iron catalyst is activated, and high-activity catalytic species are formed in situ, so that the reaction can be used for oxidizing alkene by air or oxygen under very mild conditions, and especially, the ideal catalytic effect can be obtained on complex alkene substrates.
(4) The ketone synthesized by the method has biological pharmacological activity, can be used as a medicine or a biological active molecule, is an important organic intermediate, and is widely applied to synthesis of medical intermediates, heterocycles and fine chemicals with high added values.
Detailed Description
The invention is further described with reference to specific examples.
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the detailed description of the embodiments, features and effects of the technical solutions according to the present invention is provided below.
Example 1
Synthesis of Compound 1
To a 25mL reaction flask, ferrous chloride (0.05mmol), alkene 1a (0.5mmol), triethylsilane (1.5mmol) and ethanol (2.0mL) were added sequentially in air. After mixing well at room temperature, the reaction mixture was reacted at room temperature for 6 hours. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain a yield of 98%.
Example 2
Synthesis of Compound 2
In air, a 25mL reaction flask was charged with ferrous trichloride (0.05mmol), alkene 1b (0.5mmol), triethoxysilane (1.5mmol) and methanol (2.0mL) in that order. After mixing well at room temperature, the reaction mixture was reacted under reflux for 24 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain a yield of 92%.
Example 3
Synthesis of Compound 3
To a 25mL reaction flask, iron triflate (0.05mmol), alkene 1c (0.5mmol), dimethylethoxysilane (1.5mmol) and tert-butanol (2.0mL) were added sequentially. After mixing well at room temperature, the reaction mixture was reacted under reflux for 9 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain 89% yield.
Example 4
Synthesis of Compound 4
In air, a 25mL reaction flask was charged with ferrous triflate (0.05mmol), alkene 1d (0.5mmol), polymethylhydrosiloxane (1.5mmol), isopropanol (1.5mL) and water (0.5mL) in that order. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 24 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain a yield of 90%.
Example 5
Synthesis of Compound 5
To a 25mL reaction flask, ferrous acetylacetonate (0.02mmol), ene 1e (0.5mmol), dimethylethoxysilane (2.0mmol), glycerol (1.5mL) and water (0.5mL) were added in this order in air. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 24 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain a yield of 87%.
Example 6
Synthesis of Compound 6
To a 25mL reaction flask, iron acetylacetonate (0.02mmol), alkene 1f (0.5mmol), triisopropylsilane (2.0mmol) and n-butanol (2.0mL) were sequentially added in the air. After mixing well at room temperature, the reaction mixture was reacted at 100 ℃ for 24 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain a yield of 81%.
Example 7
Synthesis of Compound 7
In an air atmosphere, ferrous chloride (0.02mmol), alkene (1 g) (0.5mmol), diethylsilane (2.0mmol), and acetonitrile (2.0mL) were sequentially added to a 25mL reaction flask. After mixing well at room temperature, the reaction mixture was reacted at 50 ℃ for 24 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain a yield of 87%.
Example 8
Synthesis of Compound 8
In air, 25mL reaction flask was charged with ferric triflate (0.02mmol), alkene 1h (0.5mmol), dichlorosilance (2.0mmol), and acetonitrile (2.0mL) in order. After mixing well at room temperature, the reaction mixture was reacted at 50 ℃ for 24 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain a yield of 90%.
Example 9
Synthesis of Compound 9
In air, 25mL of a reaction flask was charged with ferric triflate (0.02mmol), alkene 1i (0.5mmol), diisopropylchlorosilane (2.0mmol), and trifluoroethanol (2.0mL) in this order. After mixing well at room temperature, the reaction mixture was reacted at 50 ℃ for 12 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain a yield of 87%.
Example 10
Synthesis of Compound 10
In air, a 25mL reaction flask was charged with iron benzoylacetonate (0.02mmol), alkene 1j (0.5mmol), di-tert-butylsilane (2.0mmol), and polyethylene glycol-600 (2.0mL) in that order. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 12 h. After the reaction, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then separated by column chromatography to obtain 80% yield.
Example 11
Synthesis of Compound 11
In the air, 2,6, 6-tetramethyl-3, 5-heptanedionato ferrous (0.02mmol), alkene 1k (0.5mmol), diphenylchlorosilane (2.0mmol) and benzonitrile (2.0mL) were added in this order to a 25mL reaction flask. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 24 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain a yield of 81%.
Example 12
Synthesis of Compound 12
To a 25mL reaction flask, ferrous fluoride (0.02mmol), alkene 1l (0.5mmol), phenylsilane (2.0mmol), and dichloromethane (2.0mL) were added in this order under air. After mixing well at room temperature, the reaction mixture was reacted under reflux for 24 h. After the reaction, 5mL of water was added, and extraction was performed with ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure to remove the solvent, and then subjected to column chromatography to obtain 89% yield.
Example 13
Synthesis of Compound 13
In an air 25mL reaction flask were added ferrous ferricyanide (0.001mmol), limonene 1m (0.5mmol), diphenylsilane (2.0mmol), 1, 2-dichloroethane (2.0mL) in that order. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 24 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain a yield of 84%.
Example 14
Synthesis of Compound 14
In air, a 25mL reaction flask was charged with ferrous acetate (0.05mmol), alkene 1n (0.5mmol), tert-butyldimethylsilane (2.0mmol), and dimethyl sulfoxide (2.0mL) in that order. After mixing well at room temperature, the reaction mixture was reacted at 100 ℃ for 24 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain a yield of 84%.
Example 15
Synthesis of Compound 15
To a 25mL reaction flask in air was added 2,2,6, 6-tetramethyl-3, 5-heptanedionato-iron (0.05mmol), ene 1o (0.5mmol), dimethylphenylsilane (2.0mmol), and N, N-dimethylamide (2.0mL) in this order. After mixing well at room temperature, the reaction mixture was reacted at 100 ℃ for 24 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain a yield of 85%.
Example 16
Synthesis of Compound 16
To a 25mL reaction flask, 1, 3-diphenylpropanedione iron (0.05mmol), ene 1p (0.5mmol), 1, 4-bis (dimethylsilyl) benzene (2.0mmol), and ethyl acetate (2.0mL) were added in this order under air. After mixing well at room temperature, the reaction mixture was reacted under reflux for 24 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain a yield of 90%.
Example 17
Synthesis of Compound 17
To a 25mL reaction flask, 1, 3-diphenylpropanedione ferrous (0.05mmol), alkene 1q (0.5mmol), isopropoxyphenylsilane (2.0mmol), and 1, 4-dioxane (2.0mL) were sequentially added in the air. After mixing well at room temperature, the reaction mixture was reacted under reflux for 24 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain a yield of 88%.
Example 18
Synthesis of Compound 18
To a 25mL reaction flask, in order, was added ferrous benzoylacetonate (0.05mmol), alkene 1r (0.5mmol), methyldiethoxysilane (2.0mmol), and 2-pentanol (2.0 mL). After mixing well at room temperature, the reaction mixture was reacted at 100 ℃ for 24 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain a yield of 81%.
Example 19
Synthesis of Compound 19
In an air 25mL reaction flask were added ferrous benzoylacetonate (0.05mmol), limonene 1s (0.5mmol), methyldiethoxysilane (2.0mmol), sec-butanol (2.0mL) in that order. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 24 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain a yield of 84%.
Example 20
Synthesis of Compound 20
In air, a 25mL reaction flask was charged with ferric ferricyanide (0.05mmol), alkene 1t (0.5mmol), dimethylmethylhydrogen (siloxane and polysiloxane) (2.0mmol), polyethylene glycol-2000 (0.5g) and water (1.5mL) in that order. After mixing well at room temperature, the reaction mixture was reacted at 120 ℃ for 24 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain a yield of 77%.
Example 21
Synthesis of Compound 21
To a 25mL reaction flask, ferric bromide (0.05mmol), alkene 1u (0.5mmol), methylphenyl silicone oil (2.0mmol), and 4-methyl-2-pentanol (2.0mL) were added in this order under air. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 24 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain 89% yield.
Example 22
Synthesis of Compound 22
In air, a 25mL reaction flask was charged with ferrous iodide (0.05mmol), alkene 1v (0.5mmol), tris (trimethylsilyl) silane (2.0mmol), and cyclopentanol (2.0mL) in that order. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 24 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain 89% yield.
Example 23
Synthesis of Compound 23
In air, a 25mL reaction flask was charged with ferrous iodide (0.05mmol), alkene 1w (0.5mmol), tris (trimethylsilyl) silane (2.0mmol), and cyclopentanol (2.0mL) in that order. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 24 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain a yield of 71%.
Example 24
Synthesis of Compound 24
In air, ferrous iodide (0.05mmol), alkene 1X (0.5mmol), 1,1,3, 3-tetramethyldisiloxane (2.0mmol), 3-methoxybutanol (2.0mL) were added sequentially to a 25mL reaction flask. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 18 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain a yield of 84%.
Example 25
Synthesis of Compound 25
In air, ferric trichloride (0.05mmol), alkene 1y (0.5mmol), 1,1,3, 3-tetraisopropyl disiloxane (2.0mmol), and n-propanol (2.0mL) were added sequentially to a 25mL reaction flask. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 24 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain a yield of 86%.
Example 26
Synthesis of Compound 26
To a 25mL reaction flask, ferroferric oxide (0.05mmol), alkene 1z (0.5mmol), pentamethyldisiloxane (2.0mmol), and isopropanol (2.0mL) were sequentially added in the air. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 24 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain a yield of 85%.
Example 27
Synthesis of Compound 27
In air, ferrous ammonium sulfate (0.05mmol), alkene 1aa (0.5mmol), tetra (dimethylsilyl) silane (2.0mmol) and 1, 3-propanediol (2.0mL) are sequentially added into a 25mL reaction bottle. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 12 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain a yield of 85%.
Example 28
Synthesis of Compound 28
To a 25mL reaction flask in the air were added ferric fluoride (0.05mmol), alkene 1ab (0.5mmol), 1, 3-bis (3,3, 3-trifluoropropyl) -1,1,3, 3-tetramethyldisiloxane (2.0mmol), and t-butanol (2.0mL) in that order. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 24 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain a yield of 71%.
Example 29
Synthesis of Compound 29
In air, ferrous sulfate (0.05mmol), alkene 1ac (0.5mmol), 1,1,2, 2-tetraphenyldisilane (2.0mmol), and tert-butanol (2.0mL) were added sequentially to a 25mL reaction flask. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 24 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain a yield of 79%.
Example 30
Synthesis of Compound 30
In air, ferrous sulfate (0.05mmol), alkene 1ad (0.5mmol), tetrakis (dimethylsiloxy) silane (2.0mmol), and ethanol (2.0mL) were added sequentially to a 25mL reaction flask. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 18 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain 89% yield.
Example 31
Synthesis of Compound 31
To a 25mL reaction flask, iron oxalate (0.05mmol), ene 1ae (0.5mmol), tetrakis (dimethylsilyl) silane (2.0mmol), and ethanol (2.0mL) were added in this order in air. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 6 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain a yield of 88%.
Example 32
Synthesis of Compound 32
In air, a 25mL reaction flask was charged with ferrous chloride (0.05mmol), alkene 1af (0.5mmol), phenyltri (dimethylsiloxy) silane (2.0mmol), and ethanol (2.0mL) in that order. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 3 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain a yield of 95%.
Example 33
Synthesis of Compound 33
To a 25mL reaction flask, ferric chloride (0.05mmol), ene 1ag (0.5mmol), tetraphenyldisilane (2.0mmol), and tert-butanol (2.0mL) were added in this order under air. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 24 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain a yield of 90%.
Example 34
Synthesis of Compound 34
To a 25mL reaction flask, ferric chloride (0.05mmol), alkene 1ah (0.5mmol), polymethylhydrosiloxane (2.0mmol), and t-butanol (2.0mL) were added in this order in air. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 24 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain a yield of 71%.
Example 35
Synthesis of Compound 35
To a 25mL reaction flask under atmospheric pressure in oxygen was added ferrous acetylacetonate (0.05mmol), ene 1ai (0.5mmol), triethoxysilane (2.0mmol), and tert-butanol (2.0mL) in that order. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 24 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain a yield of 65%.
Example 36
Synthesis of Compound 36
Ferric acetylacetonate (0.05mmol), ene 1aj (0.5mmol), 1,1,3, 3-tetramethyldisiloxane (2.0mmol), N, N-diethylamide (1.5mL) and water (0.1mL) were added sequentially to a 25mL reaction flask under atmospheric pressure in oxygen. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 24 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain a yield of 86%.
Example 37
Synthesis of Compound 37
In a 25mL reaction flask under normal pressure in oxygen, ferrous acetylacetonate (0.05mmol), alkene 1ak (0.5mmol), 1,1,3, 3-tetramethyldisiloxane (2.0mmol) and ethanol (2.0mL) were added in this order. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 24 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain a yield of 55%.
Example 38
Synthesis of Compound 38
A25 mL reaction flask was charged with ferrous acetylacetonate (0.05mmol), alkene 1al (0.5mmol), polymethylhydrosiloxane (2.0mmol), and t-butanol (2.0mL) in this order under atmospheric pressure in oxygen. After mixing well at room temperature, the reaction mixture was reacted at 50 ℃ for 24 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain 50% yield.
Example 39
Synthesis of Compound 39
To a 25mL reaction flask, ferrous acetylacetonate (0.05mmol), ene 1am (0.5mmol), polymethylhydrosiloxane (2.0mmol), and t-butanol (2.0mL) were added in this order under atmospheric pressure in oxygen. After mixing well at room temperature, the reaction mixture was reacted at 50 ℃ for 24 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain a yield of 68%.
Example 40
Synthesis of Compound 40
To a 25mL reaction flask under normal pressure in oxygen was added ferrous acetylacetonate (0.05mmol), ene 1an (0.5mmol), polymethylhydrosiloxane (2.0mmol), and t-butanol (2.0mL) in this order. After mixing well at room temperature, the reaction mixture was reacted at 50 ℃ for 24 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain a yield of 65%.
EXAMPLE 41
Synthesis of Compound 41
Ferrous chloride (0.05mmol), alkene 1ao (0.5mmol), polymethylhydrosiloxane (2.0mmol) and ethanol (2.0mL) are sequentially added into a 25mL reaction flask under normal pressure in oxygen. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 6 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain a yield of 92%.
Example 42
Synthesis of Compound 42
Ferric chloride (0.05mmol), alkene 1ap (0.5mmol), polymethylhydrosiloxane (2.0mmol) and ethanol (2.0mL) were added sequentially to a 25mL reaction flask under atmospheric pressure in oxygen. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 6 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain a yield of 90%.
Example 43
Synthesis of Compound 43
Ferric chloride (0.05mmol), alkene 1aq (0.5mmol), polymethylhydrosiloxane (2.0mmol), and ethanol (2.0mL) were added sequentially to a 25mL reaction flask under atmospheric pressure in oxygen. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 6 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain a yield of 91%.
Example 44
Synthesis of Compound 44
Ferric chloride (0.05mmol), ene 1ar (0.5mmol), trimethoxysilane (2.0mmol) and ethanol (2.0mL) were added sequentially to a 25mL reaction flask under atmospheric pressure in oxygen. After mixing well at room temperature, the reaction mixture was reacted at 80 ℃ for 6 h. After the reaction was complete, aqueous ammonia (0.5mL) was added and stirred for 1 h. Subsequently, 5mL of water was added, and extraction was performed with diethyl ether (5 mL. times.3), and the organic phases were combined, evaporated under reduced pressure and subjected to column chromatography to obtain a yield of 94%.
The raw material and product structural formulas of examples 1-44 and the corresponding experimental results are shown in the following table:
Figure BDA0001179079100000151
Figure BDA0001179079100000161
Figure BDA0001179079100000171
Figure BDA0001179079100000181
Figure BDA0001179079100000191
although the present invention has been described in terms of the preferred embodiment, it is not intended to be limited thereto, and various iron catalysts can theoretically form highly active iron catalyst species with hydrosilane, thereby facilitating the reaction; hydrosilane is an accelerator necessary for the oxidation reaction of alkene, the silicon hydrogen reducibility of hydrosilane is utilized, and theoretically, various hydrosilanes have certain reducibility and can achieve similar effects; air or oxygen is an oxygen donor of the reaction, is an oxidant and is a reactant; the chemical bond of the alkene substrate is a carbon-carbon double bond, and substituents at two ends of the double bond influence the electron cloud density of the double bond and the steric hindrance during the reaction, namely, the modification of the substituents only influences the reaction to a certain extent and does not determine the reaction. It will be understood by those skilled in the art that the process of the present invention can be carried out while variations or modifications can be made to the corresponding embodiments without departing from the scope of the present invention, for example, substitutions, changes or modifications can be made to the substituents described within the scope of the present invention. However, any modification, equivalence and equivalent changes made to the above embodiments according to the present invention are still within the scope of the technical solution of the present invention, without departing from the spirit of the technical solution of the present invention.

Claims (5)

1. A method for synthesizing ketone by catalyzing alkylene oxide with iron is characterized in that: in an organic solvent, water or an aqueous solution of the organic solvent, using hydrosilane as an additive, air or oxygen as an oxidant and iron as a catalyst, and oxidizing alkene to prepare ketone, wherein the reaction temperature is 20-180 ℃, and the reaction time is 0.25-60 hours;
the general reaction formula is shown as follows:
Figure FDA0002362488210000011
in the formula: r' is selected from aryl, heteroaryl, hydrogen, alkyl of C1-C20, halogen substituted alkyl of C1-C20 or cycloalkyl of C3-C20;
r' is selected from hydrogen, alkyl of C1-C20, halogen substituted alkyl of C1-C20, cycloalkyl of C3-C20, fluorine, chlorine, bromine, iodine, hydroxyl, alkylcarbonyl of C1-C20, alkoxycarbonyl of C1-C20, alkylaminocarbonyl of C1-C20, arylcarbonyl, heteroaryl carbonyl or alkylsulfonyl of C1-C20;
wherein, the aryl is substituted or unsubstituted phenyl, biphenyl, naphthyl, anthryl, phenanthryl or pyrenyl;
heteroaryl in heteroaryl, heteroarylcarbonyl is selected from furyl, benzofuryl, thienyl, pyrrolyl, indolyl, carbazolyl, pyridyl, isoxazolyl, pyrazolyl, imidazolyl, oxazolyl or thiazolyl;
with R1Represents a substituent on the aryl group of R', R1Mono-or polysubstituted hydrogen on aromatic rings, R1Selected from hydrogen, C1-C20 alkyl or alkynyl, C1-C20 alkoxy, C1-C20 halogen substituted alkyl, C3-C20 cycloalkyl, aryl or aryloxy, heteroaryl, heteroaryloxy or heteroarylamino, arylcarbonyl, heteroarylcarbonyl, heteroaryloxycarbonyl, C1-C20 mercapto, fluorine, chlorine or bromine, hydroxyl, C1-C20 alkylcarbonyl, carboxyl, C1-C20 alkoxycarbonyl, C1-C20 alkylaminocarbonyl, C1-C20 alkylsulfonyl, sulfonic group, -B (OH)2Cyano or nitro;
the iron is selected from ferrous trifluoromethanesulfonate, ferric trifluoromethanesulfonate, ferrous chloride, ferrous acetylacetonate, ferric acetylacetonate, ferrous 2,2,6, 6-tetramethyl-3, 5-heptanedionate, ferrous 1, 3-diphenylpropanedionate, ferric 1, 3-diphenylpropanedionate, ferrous benzoylacetonate, ferric benzoylacetonate, ferrous ferricyanide, ferric cyanide, ferrous acetate, ferrous sulfate, ammonium sulfate, ferric sulfate, ferrous oxalate, ferric oxalate, ferrous fluoride, ferric bromide, ferrous iodide, ferric trichloride, ferric oxide or ferroferric oxide;
the hydrosilane is selected from trimethoxysilane, dimethylethoxysilane, triethylsilane, dimethylethylsilane, benzyldimethylsilane, triisopropylsilane, diethylsilane, dichlorosilance, dimethylmonochlorosilane, diisopropylchlorosilane, chloromethyl (dimethyl) silane, di-t-butylchlorosilane, diphenylchlorosilane, ethyldichlorosilane, di-t-butylsilane, methyldiphenylsilane, methyldichlorosilane, phenylsilane, diphenylsilane, triethoxysilane, t-butyldimethylsilane, dimethylphenylsilane, 1, 4-bis (dimethylsilyl) benzene, isopropoxyphenylsilane, methyldiethoxysilane, dimethoxy (methyl) silane, dimethylmethylhydrogen (siloxanes and polysiloxanes), 1,3, 3-tetraisopropyldisiloxane, dimethyldichlorosilane, 1,3, 3-dimethyldichlorosilane, 1, tris (trimethylsilyl) silane, polymethylhydrosiloxane, methylphenylsilicone oil, 1,3, 3-tetramethyldisiloxane, pentamethyldisiloxane, tetrakis (dimethylsilyl) silane, 1, 3-bis (3,3, 3-trifluoropropyl) -1,1,3, 3-tetramethyldisiloxane, tetrakis (dimethylsiloxy) silane, phenyltris (dimethylsiloxy) silane or 1,1,2, 2-tetraphenyldisilane.
2. The method for synthesizing ketone by using iron-catalyzed alkylene oxide according to claim 1, wherein: the organic solvent is selected from methanol, ethanol, ethylene glycol, N-propanol, isopropanol, 1, 3-propylene glycol, glycerol, N-butanol, isobutanol, tert-butanol, trifluoroethanol, 2-methyl-2-butanol, 3-methoxybutanol, sec-butanol, tert-amyl alcohol, 4-methyl-2-amyl alcohol, isoamyl alcohol, 2-amyl alcohol, 3-amyl alcohol, cyclopentanol, N-amyl alcohol, polyethylene glycol 200-10000, acetonitrile, benzonitrile, toluene, dichloromethane, 1, 2-dichloroethane, dimethyl sulfoxide, N-dimethylamide, N-diethylamide, ethyl acetate, 1, 4-dioxane or tetrahydrofuran.
3. The method for synthesizing ketone by using iron-catalyzed alkylene oxide according to claim 1, wherein: the volume ratio of the organic solvent to water in the aqueous solution of the organic solvent is 1: 1-100.
4. The method for synthesizing ketone by using iron-catalyzed alkylene oxide according to claim 1, wherein: the gas pressure of the air or the oxygen is 1-10 atmospheric pressure.
5. The method for synthesizing ketone by using iron-catalyzed alkylene oxide according to claim 1, wherein: the mol ratio of the alkene, the hydrosilane and the iron catalyst is 1 (0.5-50) to 0.001-10; the weight ratio of the alkene to the solvent is 1 (5-1000).
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