The solvent-free reactions of aromatic ketones and aldehydes in the presence of Zn-ZnCl2 were performed with the aid of high-speed vibration mill, Retsch MM200 mixer mill and Retsch RM100 mortar grinder to give pinaco...The solvent-free reactions of aromatic ketones and aldehydes in the presence of Zn-ZnCl2 were performed with the aid of high-speed vibration mill, Retsch MM200 mixer mill and Retsch RM100 mortar grinder to give pinacol coupling and reduction products in varying yields.展开更多
The asymmetric borane reduction of carbonyl compounds using chiral catalysts is one of the most active research. Among them,Oxazaborolidines developed by Corey are most significant- Herein. we report the use of sufony...The asymmetric borane reduction of carbonyl compounds using chiral catalysts is one of the most active research. Among them,Oxazaborolidines developed by Corey are most significant- Herein. we report the use of sufonylamides as chiral catalysts to reduce aromatic ketone in high yield and with e.e. of up to 91 %. Scheme: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
Asymmetric reduction of ct-hydroxy aromatic ketones was carded out by using carrot enzymes system, yielding corresponding chiral vicinal diols with special functional groups. The optimum reaction conditions were obtai...Asymmetric reduction of ct-hydroxy aromatic ketones was carded out by using carrot enzymes system, yielding corresponding chiral vicinal diols with special functional groups. The optimum reaction conditions were obtained after investigation of various influencing factors. Chiral aryl vicinal diols were produced with good yields and excellent enantiomeric excesses under appropriate conditions. Meanwhile, the steric factors and electronic effects of the substituents on the aromatic ring were shown to have an interesting influence on both yield and enantioselectivity.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 solid state reactions of p-nitroacetophenone, acetyl-ferrocene with indole were catalyzed by anhydrous zinc chloride or aluminum chloride, and gave exclusively the 1:2 condensation products. The solid state conden...The solid state reactions of p-nitroacetophenone, acetyl-ferrocene with indole were catalyzed by anhydrous zinc chloride or aluminum chloride, and gave exclusively the 1:2 condensation products. The solid state condensation of aromatic ketones with 1-phenyl-3-methyl-5-pyrazolone was also investigated, and the 1:1 and 2:1 condensation products were obtained. The structures of eleven new products were determined by IR, MS, H-1 NMR and elemental analysis.展开更多
A palladium-catalyzed ortho-selective C–H bond chlorination reaction for the preparation of 2-chloro aromatic ketones was described. Both electron-withdrawing and electron-donating groups on the aromatic rings are we...A palladium-catalyzed ortho-selective C–H bond chlorination reaction for the preparation of 2-chloro aromatic ketones was described. Both electron-withdrawing and electron-donating groups on the aromatic rings are well tolerated under the optimized conditions. The 2-chloro aromatic ketones obtained by our method could be applied to synthesize the derivatives of 1H-indazole or benzo[d]isoxazole.展开更多
Organoboron compounds are widely used in synthetic chemistry,pharmaceutical chemistry and material chemistry.Among various organoboron compounds,benzylboronic esters are unique and highly reactive,making them suitable...Organoboron compounds are widely used in synthetic chemistry,pharmaceutical chemistry and material chemistry.Among various organoboron compounds,benzylboronic esters are unique and highly reactive,making them suitable benzylation reagents.At present,the synthetic methods for the syntheses of benzylboronic esters are still insufficient to meet their demands.It is necessary to develop novel and practical methods for their preparation.In this work,a novel copper‐catalyzed deoxygenative gem‐hydroborylation of aromatic aldehydes and ketones has been developed.This direct and operationally simple protocol provides an effective approach for the synthesis of a variety of primary and secondary benzylboronates,in which broad functional group tolerance was presented.Widely available B2pin2(pin=pinacol)was used as the boron source and alcoholic proton was applied as the hydride source.展开更多
Novel chiral multidentate P3N4-type ligand has been synthesized and characterized by NMR and HRMS.Using i-PrOH as solvent and hydrogen source, asymmetric transfer hydrogenation of various ketones was investigated. The...Novel chiral multidentate P3N4-type ligand has been synthesized and characterized by NMR and HRMS.Using i-PrOH as solvent and hydrogen source, asymmetric transfer hydrogenation of various ketones was investigated. The catalyst generated in situ from chiral multidentate aminophosphine ligand（R,R,R,R）-3 and IrCl（CO）（PPh3）2exhibited highly catalytic activity and excellent enantioselectivity under mild conditions, achieving the corresponding chiral alcohols with up to 99% yield and 99% ee.展开更多
An unusual reduction of some aromatic aldehydes and ketones by sodium borohydride was discovered.In a THF/H2O or DMSO/H2O solvent system the aromatic aldehydes and ketones with acyloxy substituent on the orthoposition...An unusual reduction of some aromatic aldehydes and ketones by sodium borohydride was discovered.In a THF/H2O or DMSO/H2O solvent system the aromatic aldehydes and ketones with acyloxy substituent on the orthoposition to the carbonyl group can be reduced to the corresponding alkyl phenols.This unusual reduction is applicable also to the corresponding alcohols of all the above aldehydes and ketones.A putative mechanism was suggested.In addition to the above aldehydes,ketones and benzyl alcohols,certain 4acyloxybenzyl esters(probably also the 2substituted analogues)such as 4benzoyloxybenzyl benzoate was also found to be reduced to methylphenol by this unusual reduction.展开更多
The efficient catalytic systems generated in situ from RuCl2（PPh3）3 and chiral ligands N,N-bis[2-（di-o-tolylphosphino）-benzyl]cyclohexane-1,2-diamine（2） were employed for asymmetric transfer hydrogenation of aro...The efficient catalytic systems generated in situ from RuCl2（PPh3）3 and chiral ligands N,N-bis[2-（di-o-tolylphosphino）-benzyl]cyclohexane-1,2-diamine（2） were employed for asymmetric transfer hydrogenation of aromatic ketones, giving the corresponding optically active alcohols with high activities（up to 99% conversion） and excellent enantioselectivities（up to 96% e.e.） under mild conditions. The chiral ruthenium（Ⅱ） complex （R,R）-3 has been prepared and characterized by NMR and X-ray crystallography.展开更多
Methoxyacetophenone(4 MAP) was synthesized by the acylation of anisole with acetic anhydride in the presence of HY zeolite. The addition of an appropriate amount of some solvent such as dichloromethane, chloroform, c...Methoxyacetophenone(4 MAP) was synthesized by the acylation of anisole with acetic anhydride in the presence of HY zeolite. The addition of an appropriate amount of some solvent such as dichloromethane, chloroform, carbon disulfide or chlorobenzene to the reaction system can improve the yield of the acylated product to a certain extent. HY zeolite used can be recovered, and reused after being regenerated, obtaining almost the same yield of 4 MAP as the fresh zeolite.展开更多
The efficient chiral Ru 3(CO) 12 systems were prepared in situ from Ru 3(CO) 12 and various chiral diimino-or diamino-diphosphine tetradentate ligands. The systems have been used for the asymmetric transfer hy...The efficient chiral Ru 3(CO) 12 systems were prepared in situ from Ru 3(CO) 12 and various chiral diimino-or diamino-diphosphine tetradentate ligands. The systems have been used for the asymmetric transfer hydrogenation of propiophenone in 2-propanol, leading to 1-phenyl-1-propanol in a 98% yield and 96% e.e. The IR study suggests that the carbonyl hydride anion [HRu 3(CO) 11]- most probably exists as a principal species under the reaction conditions. The high chiral efficiency may be due to the synergetic effect produced by the neighboring ruthenium atoms and a special chiral micro-environment involving the polydentate ligand and the Ru 3 framework.展开更多
A quantitative interpretation of mass spectra of complex organic compounds so far is notvery perfect and needs some further investigation. In this paper a mechanism of cleft-rate-determining-steps of aromatic conjugat...A quantitative interpretation of mass spectra of complex organic compounds so far is notvery perfect and needs some further investigation. In this paper a mechanism of cleft-rate-determining-steps of aromatic conjugated polyenic acid, methyl benzoate, methyl phenyl ketone,benzonitrile and aniline is proposed, and various quantum parameters of molecular ions ofaromatic conjugated polyenic compounds, together with their framents are calculated bymeans of CNDO/2 method. Through the process of calculation, the peak-height of mass spectracan be quantitatively interpreted, which means that the main factors which influence the cleftforms of simple cleavage of mass spectra of conjugated compounds given by the authorsmight be true to some extent.展开更多
A series of novel chiral C_2-symmetric multidentate aminophosphine ligands have been successfully synthesized by Schiff-base condensation of bis（o-formylphenyl）phenylphosphane and easily available monoprotected（1R...A series of novel chiral C_2-symmetric multidentate aminophosphine ligands have been successfully synthesized by Schiff-base condensation of bis（o-formylphenyl）phenylphosphane and easily available monoprotected（1R,2R）-diaminocyclohexane.The catalytic properties of these ligands were investigated in Ir-catalyzed asymmetric transfer hydrogenation of various aromatic ketones,giving the corresponding optical active alcohols with up to 98%conversion and good ee under mild reaction conditions.展开更多
A chiral catalyst, Cp＊RhTsDPEN （Cp＊ = pentamethyl cyclopentadiene, TsDPEN = substitutive phenylsulfonyl-l,2-diphenylethylenediamine）, was synthesized and immobilized at the surface of glass. The immobilized cataly...A chiral catalyst, Cp＊RhTsDPEN （Cp＊ = pentamethyl cyclopentadiene, TsDPEN = substitutive phenylsulfonyl-l,2-diphenylethylenediamine）, was synthesized and immobilized at the surface of glass. The immobilized catalyst exhibited good catalytic efficiency for asymmetric transfer hydrogenation of aromatic ketones in water with HCOONa as hydrogen source.展开更多
文摘The solvent-free reactions of aromatic ketones and aldehydes in the presence of Zn-ZnCl2 were performed with the aid of high-speed vibration mill, Retsch MM200 mixer mill and Retsch RM100 mortar grinder to give pinacol coupling and reduction products in varying yields.
文摘The asymmetric borane reduction of carbonyl compounds using chiral catalysts is one of the most active research. Among them,Oxazaborolidines developed by Corey are most significant- Herein. we report the use of sufonylamides as chiral catalysts to reduce aromatic ketone in high yield and with e.e. of up to 91 %. Scheme:
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supported by the National Natural Science Foundation of China(No.21176203)the National Special Fund for State Key Laboratory of Bioreactor Engineering(No.2060204)the Fundamental Research Funds for the Central Universities(No.JUSRP211A12)
文摘Asymmetric reduction of ct-hydroxy aromatic ketones was carded out by using carrot enzymes system, yielding corresponding chiral vicinal diols with special functional groups. The optimum reaction conditions were obtained after investigation of various influencing factors. Chiral aryl vicinal diols were produced with good yields and excellent enantiomeric excesses under appropriate conditions. Meanwhile, the steric factors and electronic effects of the substituents on the aromatic ring were shown to have an interesting influence on both yield and enantioselectivity.
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Project supported by the National Natural Science Foundation of China and State Key Laboratory of Applied Organic Chemistry of Lanzhou University.
文摘The solid state reactions of p-nitroacetophenone, acetyl-ferrocene with indole were catalyzed by anhydrous zinc chloride or aluminum chloride, and gave exclusively the 1:2 condensation products. The solid state condensation of aromatic ketones with 1-phenyl-3-methyl-5-pyrazolone was also investigated, and the 1:1 and 2:1 condensation products were obtained. The structures of eleven new products were determined by IR, MS, H-1 NMR and elemental analysis.
基金supported by ‘973’ grant (Nos. 2011CB965300)NSFC (Nos. 21142008, 21302106)+1 种基金Tsinghua University 985 Phase Ⅱ fundsthe Tsinghua University Initiative Scientific Research Program
文摘A palladium-catalyzed ortho-selective C–H bond chlorination reaction for the preparation of 2-chloro aromatic ketones was described. Both electron-withdrawing and electron-donating groups on the aromatic rings are well tolerated under the optimized conditions. The 2-chloro aromatic ketones obtained by our method could be applied to synthesize the derivatives of 1H-indazole or benzo[d]isoxazole.
文摘Organoboron compounds are widely used in synthetic chemistry,pharmaceutical chemistry and material chemistry.Among various organoboron compounds,benzylboronic esters are unique and highly reactive,making them suitable benzylation reagents.At present,the synthetic methods for the syntheses of benzylboronic esters are still insufficient to meet their demands.It is necessary to develop novel and practical methods for their preparation.In this work,a novel copper‐catalyzed deoxygenative gem‐hydroborylation of aromatic aldehydes and ketones has been developed.This direct and operationally simple protocol provides an effective approach for the synthesis of a variety of primary and secondary benzylboronates,in which broad functional group tolerance was presented.Widely available B2pin2(pin=pinacol)was used as the boron source and alcoholic proton was applied as the hydride source.
基金the National Natural Science Foundation of China (No. 21173176)the Program for Innovative Research Team in Chinese Universities (No. IRT_14R31)+1 种基金the Fundamental Research Funds for the Central Universities (No. 20720150040)NFFTBS (No. J1310024) for financial support
文摘Novel chiral multidentate P3N4-type ligand has been synthesized and characterized by NMR and HRMS.Using i-PrOH as solvent and hydrogen source, asymmetric transfer hydrogenation of various ketones was investigated. The catalyst generated in situ from chiral multidentate aminophosphine ligand（R,R,R,R）-3 and IrCl（CO）（PPh3）2exhibited highly catalytic activity and excellent enantioselectivity under mild conditions, achieving the corresponding chiral alcohols with up to 99% yield and 99% ee.
文摘An unusual reduction of some aromatic aldehydes and ketones by sodium borohydride was discovered.In a THF/H2O or DMSO/H2O solvent system the aromatic aldehydes and ketones with acyloxy substituent on the orthoposition to the carbonyl group can be reduced to the corresponding alkyl phenols.This unusual reduction is applicable also to the corresponding alcohols of all the above aldehydes and ketones.A putative mechanism was suggested.In addition to the above aldehydes,ketones and benzyl alcohols,certain 4acyloxybenzyl esters(probably also the 2substituted analogues)such as 4benzoyloxybenzyl benzoate was also found to be reduced to methylphenol by this unusual reduction.
基金Supported by the National Natural Science Foundation of China(Nos.2042300220703034)+1 种基金the Natural Science Foundation of Fujian Province of China(No.2008J0235)the Natural Science Foundation of Guangxi Province of China(No. 0991016)
文摘The efficient catalytic systems generated in situ from RuCl2（PPh3）3 and chiral ligands N,N-bis[2-（di-o-tolylphosphino）-benzyl]cyclohexane-1,2-diamine（2） were employed for asymmetric transfer hydrogenation of aromatic ketones, giving the corresponding optically active alcohols with high activities（up to 99% conversion） and excellent enantioselectivities（up to 96% e.e.） under mild conditions. The chiral ruthenium（Ⅱ） complex （R,R）-3 has been prepared and characterized by NMR and X-ray crystallography.
文摘Methoxyacetophenone(4 MAP) was synthesized by the acylation of anisole with acetic anhydride in the presence of HY zeolite. The addition of an appropriate amount of some solvent such as dichloromethane, chloroform, carbon disulfide or chlorobenzene to the reaction system can improve the yield of the acylated product to a certain extent. HY zeolite used can be recovered, and reused after being regenerated, obtaining almost the same yield of 4 MAP as the fresh zeolite.
基金Supported by the National Natural Science Foundation of China(No.2 0 0 730 34,2 0 3730 5 6,2 0 1710 37),Fujian Provinceand Technology Comm ission(No.2 0 0 2 F0 16 ) and Xiamen Science and Technology Com mission(No.35 0 2 Z2 0 0 2 10 4 4 )
文摘The efficient chiral Ru 3(CO) 12 systems were prepared in situ from Ru 3(CO) 12 and various chiral diimino-or diamino-diphosphine tetradentate ligands. The systems have been used for the asymmetric transfer hydrogenation of propiophenone in 2-propanol, leading to 1-phenyl-1-propanol in a 98% yield and 96% e.e. The IR study suggests that the carbonyl hydride anion [HRu 3(CO) 11]- most probably exists as a principal species under the reaction conditions. The high chiral efficiency may be due to the synergetic effect produced by the neighboring ruthenium atoms and a special chiral micro-environment involving the polydentate ligand and the Ru 3 framework.
文摘A quantitative interpretation of mass spectra of complex organic compounds so far is notvery perfect and needs some further investigation. In this paper a mechanism of cleft-rate-determining-steps of aromatic conjugated polyenic acid, methyl benzoate, methyl phenyl ketone,benzonitrile and aniline is proposed, and various quantum parameters of molecular ions ofaromatic conjugated polyenic compounds, together with their framents are calculated bymeans of CNDO/2 method. Through the process of calculation, the peak-height of mass spectracan be quantitatively interpreted, which means that the main factors which influence the cleftforms of simple cleavage of mass spectra of conjugated compounds given by the authorsmight be true to some extent.
基金the National Natural Science Foundation of China(No.21173176)Program for Changjiang Scholars and Innovative Research Team in University(No.IRTl 036)State Key Laboratory of Physical Chemistry of Solid Surfaces for financial support
文摘A series of novel chiral C_2-symmetric multidentate aminophosphine ligands have been successfully synthesized by Schiff-base condensation of bis（o-formylphenyl）phenylphosphane and easily available monoprotected（1R,2R）-diaminocyclohexane.The catalytic properties of these ligands were investigated in Ir-catalyzed asymmetric transfer hydrogenation of various aromatic ketones,giving the corresponding optical active alcohols with up to 98%conversion and good ee under mild reaction conditions.
基金the Shanghai Sciences and Technologies Development Fund(Nos.13ZR1458700 and 12nm0500500)the Shanghai Municipal Education Commission(Nos.14YZ074,12ZZ135)Shanghai Normal University(Nos.DXL122,SK201329)for financial support
文摘A chiral catalyst, Cp＊RhTsDPEN （Cp＊ = pentamethyl cyclopentadiene, TsDPEN = substitutive phenylsulfonyl-l,2-diphenylethylenediamine）, was synthesized and immobilized at the surface of glass. The immobilized catalyst exhibited good catalytic efficiency for asymmetric transfer hydrogenation of aromatic ketones in water with HCOONa as hydrogen source.
