A new and simple route for the synthesis of α,β-unsaturated ketones via cleavage of the C-C(O)C single bond of monoalkylated β-diketone has been described. The reaction was catalyzed by copper, a cheap transition m...A new and simple route for the synthesis of α,β-unsaturated ketones via cleavage of the C-C(O)C single bond of monoalkylated β-diketone has been described. The reaction was catalyzed by copper, a cheap transition metal in a weakly basic medium (K<sub>3</sub>PO<sub>4</sub>) at room temperature. To carry out this study, we first had to synthesize the monoalkylated β-diketones 1. Afterwards, α,β-unsaturated ketones 2 were obtained with high yields around 80%. Finally, all the products were characterized by 1H NMR, 13C NMR, and HRMS spectra. .展开更多
Michael addition of indole and pyrrole to a variety of α, β-unsaturated ketones was efficiently promoted by a catalytic amount of GaCl3 in aqueous media to afford the corresponding products in good to excellent yields.
Microwave irradiation can accelerate the rate of the synthetic reaction of α,β-unsaturated ketones by using KF-Al2O3 as catalyst. The rate enhancement of the reaction is 360-860 fold.
Methanol is a safe, economic and easy-to-handle hydrogen source. It has rarely been used in transfer hydrogenation reactions, however. We herein report that a cyclometalated rhodium complex, rhodacycle, catalyzes high...Methanol is a safe, economic and easy-to-handle hydrogen source. It has rarely been used in transfer hydrogenation reactions, however. We herein report that a cyclometalated rhodium complex, rhodacycle, catalyzes highly chemoselective hydrogenation of α,β-unsaturated ketones with methanol as the hydrogen source. A wide variety of chalcones, styryl methyl ketones and vinyl methyl ketones, including sterically demanding ones, were reduced to the saturated ketones in refluxing methanol in a short reaction time, with no need for inter gas protection, and no reduction of the carbonyl moieties was observed. The catalysis described provides a practically easy and operationally safe method for the reduction of olefinic bonds in α,β-unsaturated ketone compounds.展开更多
The effect of catalysts P-2 00-Ni(Nickel boride) and P-2 00-Ni-M(M: Co, Fe, Cu, Sn), prepared by adopting a modified recipe, on the chemoselective hydrogenation of carbon carbon double bonds in α,β- unsaturated...The effect of catalysts P-2 00-Ni(Nickel boride) and P-2 00-Ni-M(M: Co, Fe, Cu, Sn), prepared by adopting a modified recipe, on the chemoselective hydrogenation of carbon carbon double bonds in α,β- unsaturated ketones, and the activity of catalysts P-1.80-Ni, P-2 00-Ni or P-1.80(2 00) -Ni-M(M: Pd, Co, Cu) in the selective hydrogenation of carbon carbon double bonds in α,β-unsaturated carboxylic esters, were investigated systematically. According to the experimental results, the selectivities of these catalysts toward the hydrogenation of the carbon carbon double bonds of α,β-unsaturated keones or α,β-unsaturated carboxylic esters are 96%—100% or 100%, respectively.展开更多
The reaction of α-triazolyl-α, β-unsaturated ketones with phenyl hydrazine was studied. The result indicated that cyclization took place and new heterocyclic compounds of substituted 4,5-2H-pyrazoles were obtained,...The reaction of α-triazolyl-α, β-unsaturated ketones with phenyl hydrazine was studied. The result indicated that cyclization took place and new heterocyclic compounds of substituted 4,5-2H-pyrazoles were obtained, whose structures and conformation were characterized by 1H NMR, IR, MS, elemental analysis and X-ray diffraction.展开更多
Regio and stereoselective synthesis of substituted dihydrofurans were accomplished by eeric ammonium nitrate mediated oxidative cycloaddition of 1,3-dicarbonyls to β-aryl-α,β-unsaturated ketones in moderate yields.
Catalyzed by ytterbium（III） triflate hydrate [Yb（OTf）3.xH20], the Michael addition and cyclocondensation of α,β-unsaturated ketones with active methylene compounds to afford the 1,4-adducts and benzo[b]pyran der...Catalyzed by ytterbium（III） triflate hydrate [Yb（OTf）3.xH20], the Michael addition and cyclocondensation of α,β-unsaturated ketones with active methylene compounds to afford the 1,4-adducts and benzo[b]pyran derivatives, respectively were studied.展开更多
A new synthetic method is described here to obtain α, β-unsaturated ketones through alkenes through a sequence involving f (1) cycloaddition of alkenes with dichloroketene, (2) dechlorination of adducts, (3)acidprom...A new synthetic method is described here to obtain α, β-unsaturated ketones through alkenes through a sequence involving f (1) cycloaddition of alkenes with dichloroketene, (2) dechlorination of adducts, (3)acidpromoted ring-opening isomerization ofcyclobutanones in CF3 CO2H.展开更多
The cycloaddition of N-acyliminium cations with some deactivated alkenes such as α,β-unsaturate ketones and esters has been investigated. In most cases, the N-acyliminium cations produced from 3-hydroxy-2-arylisoind...The cycloaddition of N-acyliminium cations with some deactivated alkenes such as α,β-unsaturate ketones and esters has been investigated. In most cases, the N-acyliminium cations produced from 3-hydroxy-2-arylisoindol-1-ones in the presence of BFa.OEt2 could be reacted with α,β-unsaturated ketones and esters to afford stereoselectively the cycloaddition products 6-acylisoindolo[2,1- a]quinolin-11-ones in moderate to high yields. C 2009 Wei Zhang. Published by Elsevier B.V, on behalf of Chinese Chemical Society. All rights reserved.展开更多
An efficient enantioselective Michael addition of ethyl-2-cyanoacetate and diethyl malonate to α,β-unsaturated ketones catalyzed by a simple chiral Schiff base, and products were obtained in good yields at room temp...An efficient enantioselective Michael addition of ethyl-2-cyanoacetate and diethyl malonate to α,β-unsaturated ketones catalyzed by a simple chiral Schiff base, and products were obtained in good yields at room temperature.展开更多
By ketal formation with chiral glycols like methyl or ethyl ester of tartaric acid,hydrogenation of ketals from the correspondingα,β-unsaturated 15-membered cyclic ketone produces (R)-muscone in good chemical and op...By ketal formation with chiral glycols like methyl or ethyl ester of tartaric acid,hydrogenation of ketals from the correspondingα,β-unsaturated 15-membered cyclic ketone produces (R)-muscone in good chemical and optical yield in the presence of chiral catalysts展开更多
Air-stable cationic organobismuth complexes (2-5) possessing both acidic and basic characters were synthesized. The catalyst system that comprises an air-stable bifunctional Lewis acidic/basic organobismuth complex an...Air-stable cationic organobismuth complexes (2-5) possessing both acidic and basic characters were synthesized. The catalyst system that comprises an air-stable bifunctional Lewis acidic/basic organobismuth complex and [Bmim]BF4 showed high catalytic activity, diastereoselec-tivity, stability, and reusability in the one-pot synthesis of (E)-α,β-unsaturat-ed ketones through highly selective crossed-condensation of ketones and aldehydes. Through switching the reaction from homogeneous to heterogeneous, the system shows facile separation ability and facile reusability.展开更多
In the presence of diethyl 1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylate（DHP） and a catalytic amount of potassium iodide,severalα-halo ketones were easily reduced to the corresponding ketones in acetone media....In the presence of diethyl 1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylate（DHP） and a catalytic amount of potassium iodide,severalα-halo ketones were easily reduced to the corresponding ketones in acetone media.The procedure presented here showed several merits such as short reaction time,practical experimental and isolated procedure,and excellent yields of products.展开更多
Corrosion inhibition of three α,β-unsaturated carbonyl compounds on N80 steel at high temperature and in concentrated acid medium was evaluated, and the inhibition mechanism was investigated. The results proved that...Corrosion inhibition of three α,β-unsaturated carbonyl compounds on N80 steel at high temperature and in concentrated acid medium was evaluated, and the inhibition mechanism was investigated. The results proved that both cinnamaldehyde and benzalacetone had an evident anticorrosion effect and could reduce the corrosion of steel effectively in acid medium, α,β-unsaturated carbonyl compounds with a benzene ring structure had good adsorption on steel surface. The experiments proved that polymerization of α,β-unsaturated carbonyl compounds on the steel surface at a high temperature and in concentrated acid medium resulted in a good corrosion inhibiting effect, which was attributed to the structures of α,β-unsaturated carbonyl compounds.展开更多
Two new α,β-unsaturated butyrolactone derivatives, 4-(4″-hydroxybenzyl)-3-(3′-hydroxy-phenethyl)furan-2(5H)-one (1) and 3-(3′-hydroxyphenethyl)furan-2(5H)-one (2), together with one known phenolic compound (3), w...Two new α,β-unsaturated butyrolactone derivatives, 4-(4″-hydroxybenzyl)-3-(3′-hydroxy-phenethyl)furan-2(5H)-one (1) and 3-(3′-hydroxyphenethyl)furan-2(5H)-one (2), together with one known phenolic compound (3), were isolated from the tubers of Pleione bulbocodioides (Franch.) Rolfe. Their structures were elucidated by analysis of spectroscopic data.展开更多
Ketones smoothly reacted with NBS in the presence of a catalytic amount of ptoluenesulfonic acid to give α-bromoketones in good yields in typical ionic liquids, such as [bmim]PF6 and [bmpy]Tf2N, and the ionic liquids...Ketones smoothly reacted with NBS in the presence of a catalytic amount of ptoluenesulfonic acid to give α-bromoketones in good yields in typical ionic liquids, such as [bmim]PF6 and [bmpy]Tf2N, and the ionic liquids could be repeatedly used for the same reaction after the extraction of the α-bromoketones. Then, the one-pot conversion of ketones into thiazoles by the treatment with NBS, and subsequently with thioamides could be also carried out in [bmim]PF6 and [bmpy]Tf2N, respectively Thus, [bmim]PF6 and [bmpy]Tf2N could be used as recyclable reaction media for the preparation α-bromoketones and thiazoles from ketones.展开更多
Herein we report the first[4+1]cyclization-aromatization reaction of acylsilanes andα,β-unsaturated ketones.The unprecedented visible-light-induced reaction proceeded through mild conditions without addition of any ...Herein we report the first[4+1]cyclization-aromatization reaction of acylsilanes andα,β-unsaturated ketones.The unprecedented visible-light-induced reaction proceeded through mild conditions without addition of any catalyst or additive,affording a variety of furans with broad substrate scope and good functional-group tolerance.The synthetic utility of the method was demonstrated by various downstream transformations of the otherwise difficult-to-access sulfone-containing silyl furans.The mechanism study reveals that 1,4-diketones are not likely to be the intermediates of the reaction.展开更多
Inexpensive and efficient Cu(Ⅰ) catalysis is reported for the synthesis of α-hydroxy ketones from propargylic alcohols, CO2, and water via tandem carboxylative cyclization and nucleophilic addition reaction. Notably...Inexpensive and efficient Cu(Ⅰ) catalysis is reported for the synthesis of α-hydroxy ketones from propargylic alcohols, CO2, and water via tandem carboxylative cyclization and nucleophilic addition reaction. Notably, hydration of propargylic alcohols can be carried out smoothly under atmospheric CO2 pressure, generating a series of α-hydroxy ketones efficiently and selectively. This strategy shows great potential for the preparation of valuable α-hydroxy ketones by using CO2 as a crucial cocatalyst under mild conditions.展开更多
Functionalized organozinc reagents can easily under 1, 4-addition reaction withunsaturated esters in the presence of catalytic amount of Ni (acac)_2 and tertiary ammes under verymild conditions to give the products in...Functionalized organozinc reagents can easily under 1, 4-addition reaction withunsaturated esters in the presence of catalytic amount of Ni (acac)_2 and tertiary ammes under verymild conditions to give the products in excellent yields.展开更多
文摘A new and simple route for the synthesis of α,β-unsaturated ketones via cleavage of the C-C(O)C single bond of monoalkylated β-diketone has been described. The reaction was catalyzed by copper, a cheap transition metal in a weakly basic medium (K<sub>3</sub>PO<sub>4</sub>) at room temperature. To carry out this study, we first had to synthesize the monoalkylated β-diketones 1. Afterwards, α,β-unsaturated ketones 2 were obtained with high yields around 80%. Finally, all the products were characterized by 1H NMR, 13C NMR, and HRMS spectra. .
基金support by the Natural Science Foundation of Zhejiang Province(No.Y4051137,Y405015 and Y4080177)
文摘Michael addition of indole and pyrrole to a variety of α, β-unsaturated ketones was efficiently promoted by a catalytic amount of GaCl3 in aqueous media to afford the corresponding products in good to excellent yields.
文摘Microwave irradiation can accelerate the rate of the synthetic reaction of α,β-unsaturated ketones by using KF-Al2O3 as catalyst. The rate enhancement of the reaction is 360-860 fold.
基金the Higher Committee for Education Development in Iraq for financial support(AHB)the Commonwealth Scholarships Commission in the UK for a Split-Site PhD Scholarship(RB)
文摘Methanol is a safe, economic and easy-to-handle hydrogen source. It has rarely been used in transfer hydrogenation reactions, however. We herein report that a cyclometalated rhodium complex, rhodacycle, catalyzes highly chemoselective hydrogenation of α,β-unsaturated ketones with methanol as the hydrogen source. A wide variety of chalcones, styryl methyl ketones and vinyl methyl ketones, including sterically demanding ones, were reduced to the saturated ketones in refluxing methanol in a short reaction time, with no need for inter gas protection, and no reduction of the carbonyl moieties was observed. The catalysis described provides a practically easy and operationally safe method for the reduction of olefinic bonds in α,β-unsaturated ketone compounds.
文摘The effect of catalysts P-2 00-Ni(Nickel boride) and P-2 00-Ni-M(M: Co, Fe, Cu, Sn), prepared by adopting a modified recipe, on the chemoselective hydrogenation of carbon carbon double bonds in α,β- unsaturated ketones, and the activity of catalysts P-1.80-Ni, P-2 00-Ni or P-1.80(2 00) -Ni-M(M: Pd, Co, Cu) in the selective hydrogenation of carbon carbon double bonds in α,β-unsaturated carboxylic esters, were investigated systematically. According to the experimental results, the selectivities of these catalysts toward the hydrogenation of the carbon carbon double bonds of α,β-unsaturated keones or α,β-unsaturated carboxylic esters are 96%—100% or 100%, respectively.
文摘The reaction of α-triazolyl-α, β-unsaturated ketones with phenyl hydrazine was studied. The result indicated that cyclization took place and new heterocyclic compounds of substituted 4,5-2H-pyrazoles were obtained, whose structures and conformation were characterized by 1H NMR, IR, MS, elemental analysis and X-ray diffraction.
文摘Regio and stereoselective synthesis of substituted dihydrofurans were accomplished by eeric ammonium nitrate mediated oxidative cycloaddition of 1,3-dicarbonyls to β-aryl-α,β-unsaturated ketones in moderate yields.
基金the National Natural Science Foundation of China (No.20676123) for financial support.
文摘Catalyzed by ytterbium（III） triflate hydrate [Yb（OTf）3.xH20], the Michael addition and cyclocondensation of α,β-unsaturated ketones with active methylene compounds to afford the 1,4-adducts and benzo[b]pyran derivatives, respectively were studied.
文摘A new synthetic method is described here to obtain α, β-unsaturated ketones through alkenes through a sequence involving f (1) cycloaddition of alkenes with dichloroketene, (2) dechlorination of adducts, (3)acidpromoted ring-opening isomerization ofcyclobutanones in CF3 CO2H.
基金the National Natural Science Foundation of China(No.20872056) for financial support.
文摘The cycloaddition of N-acyliminium cations with some deactivated alkenes such as α,β-unsaturate ketones and esters has been investigated. In most cases, the N-acyliminium cations produced from 3-hydroxy-2-arylisoindol-1-ones in the presence of BFa.OEt2 could be reacted with α,β-unsaturated ketones and esters to afford stereoselectively the cycloaddition products 6-acylisoindolo[2,1- a]quinolin-11-ones in moderate to high yields. C 2009 Wei Zhang. Published by Elsevier B.V, on behalf of Chinese Chemical Society. All rights reserved.
基金We appreciate the National Natural Science Foundation of China （No. 20962018, 20862015, 20762009 and 20562011） for supporting this research.
文摘An efficient enantioselective Michael addition of ethyl-2-cyanoacetate and diethyl malonate to α,β-unsaturated ketones catalyzed by a simple chiral Schiff base, and products were obtained in good yields at room temperature.
文摘By ketal formation with chiral glycols like methyl or ethyl ester of tartaric acid,hydrogenation of ketals from the correspondingα,β-unsaturated 15-membered cyclic ketone produces (R)-muscone in good chemical and optical yield in the presence of chiral catalysts
文摘Air-stable cationic organobismuth complexes (2-5) possessing both acidic and basic characters were synthesized. The catalyst system that comprises an air-stable bifunctional Lewis acidic/basic organobismuth complex and [Bmim]BF4 showed high catalytic activity, diastereoselec-tivity, stability, and reusability in the one-pot synthesis of (E)-α,β-unsaturat-ed ketones through highly selective crossed-condensation of ketones and aldehydes. Through switching the reaction from homogeneous to heterogeneous, the system shows facile separation ability and facile reusability.
基金the Guangdong Natural Science Foundation(No.8151063201000016)the National Natural Science Foundation of China(No.20672046) for financial support
文摘In the presence of diethyl 1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylate（DHP） and a catalytic amount of potassium iodide,severalα-halo ketones were easily reduced to the corresponding ketones in acetone media.The procedure presented here showed several merits such as short reaction time,practical experimental and isolated procedure,and excellent yields of products.
文摘Corrosion inhibition of three α,β-unsaturated carbonyl compounds on N80 steel at high temperature and in concentrated acid medium was evaluated, and the inhibition mechanism was investigated. The results proved that both cinnamaldehyde and benzalacetone had an evident anticorrosion effect and could reduce the corrosion of steel effectively in acid medium, α,β-unsaturated carbonyl compounds with a benzene ring structure had good adsorption on steel surface. The experiments proved that polymerization of α,β-unsaturated carbonyl compounds on the steel surface at a high temperature and in concentrated acid medium resulted in a good corrosion inhibiting effect, which was attributed to the structures of α,β-unsaturated carbonyl compounds.
文摘Two new α,β-unsaturated butyrolactone derivatives, 4-(4″-hydroxybenzyl)-3-(3′-hydroxy-phenethyl)furan-2(5H)-one (1) and 3-(3′-hydroxyphenethyl)furan-2(5H)-one (2), together with one known phenolic compound (3), were isolated from the tubers of Pleione bulbocodioides (Franch.) Rolfe. Their structures were elucidated by analysis of spectroscopic data.
文摘Ketones smoothly reacted with NBS in the presence of a catalytic amount of ptoluenesulfonic acid to give α-bromoketones in good yields in typical ionic liquids, such as [bmim]PF6 and [bmpy]Tf2N, and the ionic liquids could be repeatedly used for the same reaction after the extraction of the α-bromoketones. Then, the one-pot conversion of ketones into thiazoles by the treatment with NBS, and subsequently with thioamides could be also carried out in [bmim]PF6 and [bmpy]Tf2N, respectively Thus, [bmim]PF6 and [bmpy]Tf2N could be used as recyclable reaction media for the preparation α-bromoketones and thiazoles from ketones.
基金the National Natural Science Foundation of China(grant no.21901191)the Fundamental Research Funds for the Central Universities,and Wuhan University for financial support.
文摘Herein we report the first[4+1]cyclization-aromatization reaction of acylsilanes andα,β-unsaturated ketones.The unprecedented visible-light-induced reaction proceeded through mild conditions without addition of any catalyst or additive,affording a variety of furans with broad substrate scope and good functional-group tolerance.The synthetic utility of the method was demonstrated by various downstream transformations of the otherwise difficult-to-access sulfone-containing silyl furans.The mechanism study reveals that 1,4-diketones are not likely to be the intermediates of the reaction.
基金supported by National Natural Science Foundation of China(21672119)China Postdoctoral Science Foundation(2018M641624)~~
文摘Inexpensive and efficient Cu(Ⅰ) catalysis is reported for the synthesis of α-hydroxy ketones from propargylic alcohols, CO2, and water via tandem carboxylative cyclization and nucleophilic addition reaction. Notably, hydration of propargylic alcohols can be carried out smoothly under atmospheric CO2 pressure, generating a series of α-hydroxy ketones efficiently and selectively. This strategy shows great potential for the preparation of valuable α-hydroxy ketones by using CO2 as a crucial cocatalyst under mild conditions.
文摘Functionalized organozinc reagents can easily under 1, 4-addition reaction withunsaturated esters in the presence of catalytic amount of Ni (acac)_2 and tertiary ammes under verymild conditions to give the products in excellent yields.
