The selective hydrogenation ofα,β-unsaturated aldehydes/ketones enables precise control over product structures and properties by regulating hydrogen transport pathways and bond cleavage sequences to selectively red...The selective hydrogenation ofα,β-unsaturated aldehydes/ketones enables precise control over product structures and properties by regulating hydrogen transport pathways and bond cleavage sequences to selectively reduce C=C or C=O bonds while preserving other functional groups within the molecule.This approach serves as a critical strategy for the directional synthesis of high-value molecules.However,achieving such selectivity remains challenging due to the thermodynamic equilibrium and kinetic competition between C=O and C=C bonds inα,β-unsaturated systems.Consequently,constructing precisely targeted catalytic systems is essential to overcome these limitations,offering both fundamental scientific significance and industrial application potential.Metal-organic frameworks(MOFs)and their derivatives have emerged as innovative platforms for designing such systems,owing to their programmable topology,tunable pore microenvironments,spatially controllable active sites,and modifiable electronic structures.This review systematically summarizes the research progress of MOF-based catalysts for selec-tive hydrogenation ofα,β-unsaturated aldehydes/ketones in the last decade,with emphasis on the design strategy,conformational relationship,and catalytic mechanism,aiming to provide new ideas for the design of targeted catalyt-ic systems for the selective hydrogenation ofα,β-unsaturated aldehydes/ketones.展开更多
α-Trifluoromethyl ketones are a class of useful compounds with versatile applications.Their synthetic application via the transformation of the C—F bonds is of particular interest by allowing the synthesis of organi...α-Trifluoromethyl ketones are a class of useful compounds with versatile applications.Their synthetic application via the transformation of the C—F bonds is of particular interest by allowing the synthesis of organic compounds with diverse structures.Herein,the advances in the research areas ofα-trifluoromethyl ketone synthesis and their defluorination reactions are reviewed.Discussion on the mechanisms of the typical reactions has also been provided,in hope of affording some guides to the chemistry ofα-trifluoromethyl ketones in the synthetic methods toward themselves and their derivatives.展开更多
A direct Michael addition reaction between imidazo[1,2-a]pyridines andα,β-unsaturated ketones using acidic alumina as a C(sp3)—H acid catalyst has been developed.The abundant C(sp3)—H acid sites(Al^(3+))on the aci...A direct Michael addition reaction between imidazo[1,2-a]pyridines andα,β-unsaturated ketones using acidic alumina as a C(sp3)—H acid catalyst has been developed.The abundant C(sp3)—H acid sites(Al^(3+))on the acidic alumina surface effectively activate the carbonyl group ofα,β-unsaturated ketones,significantly enhancing the electrophilicity of theβ-carbon and thereby facilitating selective alkylation at the C3 position of imidazo[1,2-a]pyridines.This method demonstrates excellent functional group compatibility,mild reaction conditions,low reagent costs,and operational simplicity,providing a novel strategy for the efficient synthesis of alkylated imidazo[1,2-a]pyridine derivatives.展开更多
C-C coupling and hydrodeoxygenation are two important reactions in the production of sustainable aviation fuels(SAFs)with lignocellulose derived oxygenates.However,it is challenging to integrate them into a one-step p...C-C coupling and hydrodeoxygenation are two important reactions in the production of sustainable aviation fuels(SAFs)with lignocellulose derived oxygenates.However,it is challenging to integrate them into a one-step process because the necessity of oxygen containing functional groups in the C-C coupling reactions.Herein,jet fuel range polycycloalkanes and branched alkanes were directly synthesized by a cascade self-aldol condensation/hydrodeoxygenation reaction of lignocellulosic ketones over a zirconium phosphate loaded calcium modified nickel catalyst(NiCa/ZrP)that was prepared by a simple incipient impregnation method.Compared with the catalyst systems that have been reported in literature,the NiCa/ZrP catalyst have many advantages such as fewer step,easier operation and preparation,lower equipment investment and cost,wider applicability,etc.Moreover,the NiCa/ZrP is also applicable for the direct production of jet fuel range alkanes with lignocellulosic ketones and/or alcohols by a cascade dehydrogenation/aldol condensation/hydrodeoxygenation reaction.This work gives a new idea about the reduction of energy consumption and cost by catalyst designing in the manufacture of SAFs from lignocellulose.展开更多
A combination of tetrachlorosilane(TCS) and phenol in dichloromethane was found to be an efficient reagent for hydro-chlorination ofα,β-unsaturated ketones to afford the correspondingβ-chloroketones in good yield...A combination of tetrachlorosilane(TCS) and phenol in dichloromethane was found to be an efficient reagent for hydro-chlorination ofα,β-unsaturated ketones to afford the correspondingβ-chloroketones in good yield at ambient temperature. Reactions of the titled compounds with TCS-NaN_3 as well as with nitriles utilizing TCS-ZnCl_2 to give 1,5-disubstituted tetrazole derivatives orβ-amido ketones respectively are also described.展开更多
A reaction of α-bromo aromatic ketones in water with microwave irradiation gave the corresponding α-hydroxy aromatic ketones in good yields. The use of microwaves was found to significantly improve yields and shorte...A reaction of α-bromo aromatic ketones in water with microwave irradiation gave the corresponding α-hydroxy aromatic ketones in good yields. The use of microwaves was found to significantly improve yields and shorten the reaction time. This reaction afforded a very clean, convenient method for the synthesis of α-hydroxy aromatic ketones.展开更多
Cerium trichloride heptahydrate(CeCl_3·7H_2O) was found to be an efficient and recyclable catalyst for the three-component direct Mannich reaction of anilines and benzaldehydes with acetophenone.This protocol has...Cerium trichloride heptahydrate(CeCl_3·7H_2O) was found to be an efficient and recyclable catalyst for the three-component direct Mannich reaction of anilines and benzaldehydes with acetophenone.This protocol has advantages of high yield,no environmental pollution,mild condition,and simple work-up procedure.展开更多
The efficient, green, facile, mild and straightforward conversion procedure for the oxidation of cyclic ketones to lactones at room temperature utilizing potassium peroxydisulfate (K2S2O8) in acidic media is satisfa...The efficient, green, facile, mild and straightforward conversion procedure for the oxidation of cyclic ketones to lactones at room temperature utilizing potassium peroxydisulfate (K2S2O8) in acidic media is satisfactory to high yields without using traditional chlorinated solvents is reported. This oxidative reagent is cheap and friendly environmental procedure for industrial purposes than use of organic peracids.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.
Aromatic aldehydes undergo crossed-aldol condensation with ketones in the presence of catalytic amount of sulfamic acid (SA) to afford the corresponding α,β-unsaturated aldol products under solvent-free conditions...Aromatic aldehydes undergo crossed-aldol condensation with ketones in the presence of catalytic amount of sulfamic acid (SA) to afford the corresponding α,β-unsaturated aldol products under solvent-free conditions in good to high yields at 45-80 ℃.展开更多
Green,mild and efficient iodination of hydroxylated aromatic aldehydes and ketones using iodine and iodic acid in the solidstate by grinding under solvent-free conditions at room temperature.This method provides sever...Green,mild and efficient iodination of hydroxylated aromatic aldehydes and ketones using iodine and iodic acid in the solidstate by grinding under solvent-free conditions at room temperature.This method provides several advantages such as environmentally friendly,short reaction times,high yields,non-hazardous and simple work-up procedure.展开更多
The 1,2-dibromoethane-and Kl-mediatedα-acyloxylation of ketones is reported in moderate to good yield without the use of transition metals and strong oxidants.Various acids are well tolerated with wide functional gro...The 1,2-dibromoethane-and Kl-mediatedα-acyloxylation of ketones is reported in moderate to good yield without the use of transition metals and strong oxidants.Various acids are well tolerated with wide functional group compatibility.An 1,2-dibromoethane-and Kl-catalysed reaction mechanism is proposed based on the results of control experiments.展开更多
The rate constants for the C1 atom reaction with three branched ketones have been measured at 298 ± 2 K and 760 Torr using the relative rate method in the absence of NO. The rate constants values obtained (in un...The rate constants for the C1 atom reaction with three branched ketones have been measured at 298 ± 2 K and 760 Torr using the relative rate method in the absence of NO. The rate constants values obtained (in units of 10^-10 cm^3/(molecule.sec)) are: k(2-methyl-3-pentanone) = 1.07 ± 0.26, k(3-methyl-2-pentanone) =1.21 ± 0.26, and k(4-methyl-2-pentanone) = 1.35 ± 0.27. Combining the chemical kinetic data obtained by this study with those reported for other ketones, a revised Structure Activity Relationship (SAR) parameter and R group reactivity (kR of R(O)R' and CHx (x = 1, 2, 3) group reactivity (kCHx) toward C1 atoms were proposed. In addition, the products from the three reactions in the presence of NO were also identified and quantified by using PTR-ToF-MS and GC-FID, and the yields of the identified products are: acetone (39% ± 8%) + ethanal (78% ± 12%), 2-butanone (22% ± 2%) + ethanal (75% ± 10%) + propanal (14% ± 1%) and acetone (26% ± 3%) + 2-methylpmpanal (24% ± 2%), for C1 atoms reaction with 2-methyl-3-pentanone, 3-methyl-2-pentanone and 4-methyl-2-pentanone, respectively. Based on the obtained results, the reaction mechanisms of C1 atoms with these three ketones are proposed.展开更多
Both aliphatic and aromatic ketones are efficiently transfer-hydrogenated by propan-2-ol under mild conditions in the presence of a catalytic amount of poly(2,6-dimethyl-1,4-Phenylene oxide) (PPO) anchored ruthenium...Both aliphatic and aromatic ketones are efficiently transfer-hydrogenated by propan-2-ol under mild conditions in the presence of a catalytic amount of poly(2,6-dimethyl-1,4-Phenylene oxide) (PPO) anchored ruthenium complex and sodium hydroxide. An important feature of this polymer anchored catalyst is its stability in air.展开更多
The asymmetric transfer hydrogenation(ATH)of a wide range of ketones catalyzed by manganese complex as well as chiral P_(x)N_(y)-type ligand under mild conditions was investigated.Using 2-propanol as hydrogen source,v...The asymmetric transfer hydrogenation(ATH)of a wide range of ketones catalyzed by manganese complex as well as chiral P_(x)N_(y)-type ligand under mild conditions was investigated.Using 2-propanol as hydrogen source,various ketones could be enantioselectively hydrogenated by combining cheap,readily available[MnBr(CO)_(5)]with chiral,22-membered macrocyclic ligand(R,R,R',R')-CyP_(2)N_(4)(L_(5))with 2 mol%of catalyst loading,affording highly valuable chiral alcohols with up to 95%ee.展开更多
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
A CrO3 catalyzed oxidation of homopropargyl alcohols with tert-butyl hydroperoxide under microwave irradiation was found to be an efficient and rapid alternative for the preparation of 1,2-allenic ketones.The advantag...A CrO3 catalyzed oxidation of homopropargyl alcohols with tert-butyl hydroperoxide under microwave irradiation was found to be an efficient and rapid alternative for the preparation of 1,2-allenic ketones.The advantages of this procedure include short reaction time,less adverse impact on the environment and reasonably high efficiency.展开更多
An easy and rapid method for the α-bromination of ketones using N-bromosuccinimide (NBS) catalyzed by silica gel in methanol under reflux conditions was developed. The expected products were formed in excellent iso...An easy and rapid method for the α-bromination of ketones using N-bromosuccinimide (NBS) catalyzed by silica gel in methanol under reflux conditions was developed. The expected products were formed in excellent isolated yields within a short period of time (5-20 min). Major advantages of the present procedure include use of inexpensive and readily available catalyst, exclusion of pre- and post-chemical treatment of catalyst and use of methanol as solvent instead of ethers and chlorinated solvents.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
文摘The selective hydrogenation ofα,β-unsaturated aldehydes/ketones enables precise control over product structures and properties by regulating hydrogen transport pathways and bond cleavage sequences to selectively reduce C=C or C=O bonds while preserving other functional groups within the molecule.This approach serves as a critical strategy for the directional synthesis of high-value molecules.However,achieving such selectivity remains challenging due to the thermodynamic equilibrium and kinetic competition between C=O and C=C bonds inα,β-unsaturated systems.Consequently,constructing precisely targeted catalytic systems is essential to overcome these limitations,offering both fundamental scientific significance and industrial application potential.Metal-organic frameworks(MOFs)and their derivatives have emerged as innovative platforms for designing such systems,owing to their programmable topology,tunable pore microenvironments,spatially controllable active sites,and modifiable electronic structures.This review systematically summarizes the research progress of MOF-based catalysts for selec-tive hydrogenation ofα,β-unsaturated aldehydes/ketones in the last decade,with emphasis on the design strategy,conformational relationship,and catalytic mechanism,aiming to provide new ideas for the design of targeted catalyt-ic systems for the selective hydrogenation ofα,β-unsaturated aldehydes/ketones.
文摘α-Trifluoromethyl ketones are a class of useful compounds with versatile applications.Their synthetic application via the transformation of the C—F bonds is of particular interest by allowing the synthesis of organic compounds with diverse structures.Herein,the advances in the research areas ofα-trifluoromethyl ketone synthesis and their defluorination reactions are reviewed.Discussion on the mechanisms of the typical reactions has also been provided,in hope of affording some guides to the chemistry ofα-trifluoromethyl ketones in the synthetic methods toward themselves and their derivatives.
文摘A direct Michael addition reaction between imidazo[1,2-a]pyridines andα,β-unsaturated ketones using acidic alumina as a C(sp3)—H acid catalyst has been developed.The abundant C(sp3)—H acid sites(Al^(3+))on the acidic alumina surface effectively activate the carbonyl group ofα,β-unsaturated ketones,significantly enhancing the electrophilicity of theβ-carbon and thereby facilitating selective alkylation at the C3 position of imidazo[1,2-a]pyridines.This method demonstrates excellent functional group compatibility,mild reaction conditions,low reagent costs,and operational simplicity,providing a novel strategy for the efficient synthesis of alkylated imidazo[1,2-a]pyridine derivatives.
基金supported by the National Key R&D Program of China(2022YFB4201802)the National Natural Science Foundation of China(22178335)DICP(DICP I202448)。
文摘C-C coupling and hydrodeoxygenation are two important reactions in the production of sustainable aviation fuels(SAFs)with lignocellulose derived oxygenates.However,it is challenging to integrate them into a one-step process because the necessity of oxygen containing functional groups in the C-C coupling reactions.Herein,jet fuel range polycycloalkanes and branched alkanes were directly synthesized by a cascade self-aldol condensation/hydrodeoxygenation reaction of lignocellulosic ketones over a zirconium phosphate loaded calcium modified nickel catalyst(NiCa/ZrP)that was prepared by a simple incipient impregnation method.Compared with the catalyst systems that have been reported in literature,the NiCa/ZrP catalyst have many advantages such as fewer step,easier operation and preparation,lower equipment investment and cost,wider applicability,etc.Moreover,the NiCa/ZrP is also applicable for the direct production of jet fuel range alkanes with lignocellulosic ketones and/or alcohols by a cascade dehydrogenation/aldol condensation/hydrodeoxygenation reaction.This work gives a new idea about the reduction of energy consumption and cost by catalyst designing in the manufacture of SAFs from lignocellulose.
文摘A combination of tetrachlorosilane(TCS) and phenol in dichloromethane was found to be an efficient reagent for hydro-chlorination ofα,β-unsaturated ketones to afford the correspondingβ-chloroketones in good yield at ambient temperature. Reactions of the titled compounds with TCS-NaN_3 as well as with nitriles utilizing TCS-ZnCl_2 to give 1,5-disubstituted tetrazole derivatives orβ-amido ketones respectively are also described.
基金financially supported by the National Special Fund for State Key Laboratory of Bioreactor Engineering(No.2060204)the National Natural Science Foundation of China(No.20672037)
文摘A reaction of α-bromo aromatic ketones in water with microwave irradiation gave the corresponding α-hydroxy aromatic ketones in good yields. The use of microwaves was found to significantly improve yields and shorten the reaction time. This reaction afforded a very clean, convenient method for the synthesis of α-hydroxy aromatic ketones.
基金the financial support from Nanjing University of Science and Technology.
文摘Cerium trichloride heptahydrate(CeCl_3·7H_2O) was found to be an efficient and recyclable catalyst for the three-component direct Mannich reaction of anilines and benzaldehydes with acetophenone.This protocol has advantages of high yield,no environmental pollution,mild condition,and simple work-up procedure.
基金support and purchase of Hewlett-Packard 6890 GC-Hewlett-Packard 5973N MSD instrument.
文摘The efficient, green, facile, mild and straightforward conversion procedure for the oxidation of cyclic ketones to lactones at room temperature utilizing potassium peroxydisulfate (K2S2O8) in acidic media is satisfactory to high yields without using traditional chlorinated solvents is reported. This oxidative reagent is cheap and friendly environmental procedure for industrial purposes than use of organic peracids.
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Aromatic aldehydes undergo crossed-aldol condensation with ketones in the presence of catalytic amount of sulfamic acid (SA) to afford the corresponding α,β-unsaturated aldol products under solvent-free conditions in good to high yields at 45-80 ℃.
文摘Green,mild and efficient iodination of hydroxylated aromatic aldehydes and ketones using iodine and iodic acid in the solidstate by grinding under solvent-free conditions at room temperature.This method provides several advantages such as environmentally friendly,short reaction times,high yields,non-hazardous and simple work-up procedure.
基金the Drug Innovation Major Project(No.2018ZX09711001-001-001)CAMS Innovation Fund for Medical Sciences(CIFMS)(No.2016-I2M-1-010)for financial support。
文摘The 1,2-dibromoethane-and Kl-mediatedα-acyloxylation of ketones is reported in moderate to good yield without the use of transition metals and strong oxidants.Various acids are well tolerated with wide functional group compatibility.An 1,2-dibromoethane-and Kl-catalysed reaction mechanism is proposed based on the results of control experiments.
基金supported by Labex Voltaire (ANR-10-LABX-100-01), ARD PIVOTS program (supported by the Centre-Val de Loire regional council)the European Union's Horizon 2020 Research and Innovation Programme through the EUROCHAMP2020 Infrastructure Activity under grant agreement No. 730997+1 种基金the China Scholarship Council for the financial supportsupported by the Natural Science Foundation of China (No. 41305124)
文摘The rate constants for the C1 atom reaction with three branched ketones have been measured at 298 ± 2 K and 760 Torr using the relative rate method in the absence of NO. The rate constants values obtained (in units of 10^-10 cm^3/(molecule.sec)) are: k(2-methyl-3-pentanone) = 1.07 ± 0.26, k(3-methyl-2-pentanone) =1.21 ± 0.26, and k(4-methyl-2-pentanone) = 1.35 ± 0.27. Combining the chemical kinetic data obtained by this study with those reported for other ketones, a revised Structure Activity Relationship (SAR) parameter and R group reactivity (kR of R(O)R' and CHx (x = 1, 2, 3) group reactivity (kCHx) toward C1 atoms were proposed. In addition, the products from the three reactions in the presence of NO were also identified and quantified by using PTR-ToF-MS and GC-FID, and the yields of the identified products are: acetone (39% ± 8%) + ethanal (78% ± 12%), 2-butanone (22% ± 2%) + ethanal (75% ± 10%) + propanal (14% ± 1%) and acetone (26% ± 3%) + 2-methylpmpanal (24% ± 2%), for C1 atoms reaction with 2-methyl-3-pentanone, 3-methyl-2-pentanone and 4-methyl-2-pentanone, respectively. Based on the obtained results, the reaction mechanisms of C1 atoms with these three ketones are proposed.
文摘Both aliphatic and aromatic ketones are efficiently transfer-hydrogenated by propan-2-ol under mild conditions in the presence of a catalytic amount of poly(2,6-dimethyl-1,4-Phenylene oxide) (PPO) anchored ruthenium complex and sodium hydroxide. An important feature of this polymer anchored catalyst is its stability in air.
基金the National Natural Science Foundation of China(No.21673190)for financial support。
文摘The asymmetric transfer hydrogenation(ATH)of a wide range of ketones catalyzed by manganese complex as well as chiral P_(x)N_(y)-type ligand under mild conditions was investigated.Using 2-propanol as hydrogen source,various ketones could be enantioselectively hydrogenated by combining cheap,readily available[MnBr(CO)_(5)]with chiral,22-membered macrocyclic ligand(R,R,R',R')-CyP_(2)N_(4)(L_(5))with 2 mol%of catalyst loading,affording highly valuable chiral alcohols with up to 95%ee.
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.
基金the National Natural Science Foundation of China(Nos20772025 and 20972042)Innovation Scientists and Technicians Troop Construction Projects of Henan Province(No104100510019)+1 种基金Natural Science Foundation of Henan Province(No092300410237)the Natural Science Foundation of Department of Education of Henan Province(Nos2009A150017 and 2008A150013)
文摘A CrO3 catalyzed oxidation of homopropargyl alcohols with tert-butyl hydroperoxide under microwave irradiation was found to be an efficient and rapid alternative for the preparation of 1,2-allenic ketones.The advantages of this procedure include short reaction time,less adverse impact on the environment and reasonably high efficiency.
基金Council of Scientific and Industrial Research(CSIR),New Delhi,Government of India for thefinancial support under major research project(No.01(2391)/10/EMR-II)
文摘An easy and rapid method for the α-bromination of ketones using N-bromosuccinimide (NBS) catalyzed by silica gel in methanol under reflux conditions was developed. The expected products were formed in excellent isolated yields within a short period of time (5-20 min). Major advantages of the present procedure include use of inexpensive and readily available catalyst, exclusion of pre- and post-chemical treatment of catalyst and use of methanol as solvent instead of ethers and chlorinated solvents.
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.