Ketoesters were successfully utilized as the bifunctionalization reagents to react with diaryl alkynes under visible light and photocatalyst or additives free conditions. A series of phenanthrenes containing acyl and ...Ketoesters were successfully utilized as the bifunctionalization reagents to react with diaryl alkynes under visible light and photocatalyst or additives free conditions. A series of phenanthrenes containing acyl and ester groups were obtained in high yields. This protocol features with excellent regioselectivity, high efficiency, and atomic economy.展开更多
The visible light promoted C-H sulfonylmethylation of imidazopyridines with easily accessible bromomethyl sulfones under mild reaction conditions was described.This protocol provides an effective and practical access ...The visible light promoted C-H sulfonylmethylation of imidazopyridines with easily accessible bromomethyl sulfones under mild reaction conditions was described.This protocol provides an effective and practical access to sulfonylmethylated imidazopyridines with good functional group tolerance.The desired products were provided in moderate to excellent yields for 50 examples at room temperature.The method could also be an attractive strategy to install a methyl group on imidazopyridines.展开更多
Rhodium(Ⅲ)-catalyzed synthesis of indole derivatives has been realized via cascade reaction of C -H alkylation/nucleophilic cyclization starting from readily available N-phenylpyridin-2-amines and sulfoxonium ylides....Rhodium(Ⅲ)-catalyzed synthesis of indole derivatives has been realized via cascade reaction of C -H alkylation/nucleophilic cyclization starting from readily available N-phenylpyridin-2-amines and sulfoxonium ylides. Notably, this transformation could smoothly proceed with high yields, good regioselectivity, and feature broad group tolerance and under redox-neutral condition to avoid external oxidant. The titled products are potentially important building blocks in the organic synthesis through various chemical transformations.展开更多
A selective ring-opening [3+2] cyclization reaction of benzo[d]isoxazoles with 2-bromo-propanamides has been developed.The azaoxyallyl cation intermediates are employed as C^O 3-atom synthon to build oxa-heterocycles ...A selective ring-opening [3+2] cyclization reaction of benzo[d]isoxazoles with 2-bromo-propanamides has been developed.The azaoxyallyl cation intermediates are employed as C^O 3-atom synthon to build oxa-heterocycles via the selectivity of suitable cyclization partners.This transformation provides rapid access to highly functionalized 2-hydroxyaryl-oxazolines under mild conditions and excellent regioselectivity.展开更多
Anthrones are key structural motifs in many natural products, bioactive compounds and pharmaceutical chemicals. Earth-abundant-metal-catalyzed asymmetric functionalization of anthrones has not proved to be viable. Her...Anthrones are key structural motifs in many natural products, bioactive compounds and pharmaceutical chemicals. Earth-abundant-metal-catalyzed asymmetric functionalization of anthrones has not proved to be viable. Herein, we disclosed a highly enantioselective propargylic substitution of anthrones with propargylic esters using copper salts with chiral N, N, P-ligand. This strategy is amenable to a broad range of substrates, uses readily available starting materials, provides excellent yields with remarkable enantioselectivity under mild conditions, and enables attractive products diversification routes.展开更多
A novel approach for the synthesis of 4-aminoquinazolines has been developed via rhodium(Ⅲ)-catalyzed [4+2] annulation of N-arylbenzamidines with 1,4,2-dioxazol-5-ones.This reaction features excellent regioselectivit...A novel approach for the synthesis of 4-aminoquinazolines has been developed via rhodium(Ⅲ)-catalyzed [4+2] annulation of N-arylbenzamidines with 1,4,2-dioxazol-5-ones.This reaction features excellent regioselectivity,broad substrate scope and high step economy,which would provide the refe rence for the construction of the fused 4-aminoquinazolines with biologically and pharmacologically active compounds.展开更多
A green tandem reaction,including insertion/aerobic oxidation/bisindolylation,starting from indoles and diazo compounds has been developed.The combination of water and fluorinated alcohol plays dual roles as solvent a...A green tandem reaction,including insertion/aerobic oxidation/bisindolylation,starting from indoles and diazo compounds has been developed.The combination of water and fluorinated alcohol plays dual roles as solvent and promoter in this chemical transformation.Molecular oxygen in the air acts as an oxidant.3,3’-Bis(indolyl)methanes with quaternary carbon were produced under metal-free conditions.No any catalyst and additive were required.N2 and water were released as sole by-products.Absence of water and fluorinated alcohol resulted in Wolff rearrangement product.展开更多
A ferrocene-initiated radical reaction of benzoquinone with amines has been successfully developed for the direct access to diaminobenzoquinone imines in high yields,in which the comme rcially available and cheap ferr...A ferrocene-initiated radical reaction of benzoquinone with amines has been successfully developed for the direct access to diaminobenzoquinone imines in high yields,in which the comme rcially available and cheap ferrocene was employed as a radical initiator and TBHP was used as an oxidant.Moreover,this reaction could be achieved with low loading of ferrocene(0.5 mol%).This protocol is highly efficient with good substrate tolera nce and provides a new approach for the construction of benzoquinone imines with potential pharmaceutical interest.展开更多
As balanced electron-rich P,C-chelating ligands,phosphine-phosphonium-ylides are considered for their ability to in situ promote palladium-catalysed direct C(sp^2)—H arylation.Using methyl phosphonium salts of 2,2’-...As balanced electron-rich P,C-chelating ligands,phosphine-phosphonium-ylides are considered for their ability to in situ promote palladium-catalysed direct C(sp^2)—H arylation.Using methyl phosphonium salts of 2,2’-bis(diphenylphosphino)-1,1’-binaphtyl("methyl-BINAPIUM")as ylide precursors under optimized reaction conditions,arylation of benzoxazole was found to proceed in moderate to high yield to give functional 2-aryl benzoxazoles.A strong anion effect of the non-salt free ylide was evidenced(TfO^->I^->PF6^-≈salt-free).This first example of phosphonium ylides as ligands in catalytic C-H activation extends the prospect of their general implementation in homogeneous transition metal catalysis.展开更多
A Ru(Ⅲ)-catalyzed annulation reaction of 2-aminoaromatic aldehydes(ketones)and isoxazoles to afford diverse 3-cyanoquinolines has been developed.Notably,isoxazole acted as a cyclization reagent and nontoxic cyano sou...A Ru(Ⅲ)-catalyzed annulation reaction of 2-aminoaromatic aldehydes(ketones)and isoxazoles to afford diverse 3-cyanoquinolines has been developed.Notably,isoxazole acted as a cyclization reagent and nontoxic cyano source via N-O bond cleavage and fragmentation.Variously substituted(especially 6-or 7-substituted)quinolines could be easily afforded.This procedure features wide functional group compatibility,efficiency and avoiding toxic cyano source.Meanwhile,this protocol could be successfully applied to scale-up synthesis.Further chemical transformations of 3-cyanoquinoline could give some valuable skeletons,demonstrating its potential in synthetic application.展开更多
Rhodium(Ⅲ)-catalyzed[4+1]cyclization of azobenzenes with α-Cl ketones has been developed.3-Acyl-2H-indazoles could be easily afforded in up to 97%yields for more than 30 examples.The obtained products are potentiall...Rhodium(Ⅲ)-catalyzed[4+1]cyclization of azobenzenes with α-Cl ketones has been developed.3-Acyl-2H-indazoles could be easily afforded in up to 97%yields for more than 30 examples.The obtained products are potentially valuable in organic synthesis and drug discovery.This protocol featured with high efficiency,extensive functional group tolerance and mild reaction conditions.The one-step efficient construction of an anti-inflammatory agent confirms the practicability of this procedure.展开更多
Cp^*Co(Ⅲ)-catalyzed direct C—H amidation of azines has been developed.This co nversion could proceed smoothly in the absence of external oxidants,acids or bases,with excellent regioselectivity and broad functional g...Cp^*Co(Ⅲ)-catalyzed direct C—H amidation of azines has been developed.This co nversion could proceed smoothly in the absence of external oxidants,acids or bases,with excellent regioselectivity and broad functional group tolerance,CO2 was released as the sole byproduct,thus providing an environmentally benign amidation process.The products obtained are important intermediates in organic synthesis.展开更多
Pd-catalyzed oxidative homocoupling of 2-arylquinazolinones was successfully developed for the direct construction of biaryls via C—H bond activation.New well-defined structure that possessed two quinazolinone units ...Pd-catalyzed oxidative homocoupling of 2-arylquinazolinones was successfully developed for the direct construction of biaryls via C—H bond activation.New well-defined structure that possessed two quinazolinone units was obtained with high efficiency and atomic economy.The protocols offer an efficient approach to the synthetically useful and functionalized biaryls in good yields using quinazolinone as a directing group.展开更多
An Ir-catalyzed selective mono-sulfamidation of 2-arylquinazolinones has been achieved with a low catalyst loading under mild conditions.A series of regioselective mono-sulfamided 2-arylquinazolinones were obtained in...An Ir-catalyzed selective mono-sulfamidation of 2-arylquinazolinones has been achieved with a low catalyst loading under mild conditions.A series of regioselective mono-sulfamided 2-arylquinazolinones were obtained in up to 90%yields.Compared with our previous work of constructing di-sulfamidated 2-arylquinazolinones,the mono-sulfamided products could be obtained selectively by changing the ratio of substrates,the loading of catalyst,acid additive,and reaction time.展开更多
We herein report a highly regioselective rhodium-catalyzed C6-and C7—H bond functionalization of indolines with alkynes by using 2-pyrimidine as a directing group. Moreover, NH-free benzo[g]indole unit could be obtai...We herein report a highly regioselective rhodium-catalyzed C6-and C7—H bond functionalization of indolines with alkynes by using 2-pyrimidine as a directing group. Moreover, NH-free benzo[g]indole unit could be obtained by an oxidation/removal of the directing group sequence.展开更多
In 1998.Paul Anastas and John Warner defined 12 Principles of Green Chemistry,aiming at cleaner processes,safer products and increasing use of renewable rather than fossil resources.With the growing awareness of envir...In 1998.Paul Anastas and John Warner defined 12 Principles of Green Chemistry,aiming at cleaner processes,safer products and increasing use of renewable rather than fossil resources.With the growing awareness of environmental issues,the international chemical community is driven to develop novel and environmentally friendly synthetic strategies for the replacement of inefficient and pollutional chemical processes.Delightedly,a lot of eco-friendly synthetic methodologies have been established over the past decades.展开更多
A visible-light-promoted formal[2+2+1]cyclization of N-aryl glycines with quinoxalin-2(1H)-ones to synthesize tetrahydroimidazo[1,5-a]quinoxalin-4(5H)-ones have been developed.The protocol features operational simplic...A visible-light-promoted formal[2+2+1]cyclization of N-aryl glycines with quinoxalin-2(1H)-ones to synthesize tetrahydroimidazo[1,5-a]quinoxalin-4(5H)-ones have been developed.The protocol features operational simplicity,mild reaction conditions with blue LED light employing Ru(bpy)3Cl2.6H2O as a photoredox catalyst,a combination of O2 from air and Cu(OAc)2 as the oxidant and broad substrate applicability.展开更多
Due to using （R）- or （S）-a-methylbenzylamine as a chiral auxiliary, and low-temperature regime for reduction of the intermediate ferrocenyl-mono- or 1,1＇-bis-ketimines, the corresponding secondary mono- or 1,1＇-...Due to using （R）- or （S）-a-methylbenzylamine as a chiral auxiliary, and low-temperature regime for reduction of the intermediate ferrocenyl-mono- or 1,1＇-bis-ketimines, the corresponding secondary mono- or 1,1＇-bis-amines were prepared with high diastereoselectivity. Removal of the a-methylbenzyl group afforded the optically active primary mono- and bis-ferrocenylethylamines in high yields. The absolute configuration of （R,R）-3a and （S,S）-3b was determined by X-ray single crystal diffraction.展开更多
Photoredox-catalyzed generation of sulfonated oxazolines starting from N-allylamides,DABCO·(SO2)2,and aryldiazonium salts has been developed.A range of sulfonated oxazolines were obtained in moderate to good yiel...Photoredox-catalyzed generation of sulfonated oxazolines starting from N-allylamides,DABCO·(SO2)2,and aryldiazonium salts has been developed.A range of sulfonated oxazolines were obtained in moderate to good yields.This transformation involves the sequential insertion of sulfur dioxide,intermolecular sulfonylation of alkenes and intramolecular cyclization via a radical process.This protocol features good compatibility of functional groups and mild reaction conditions.Sulfonated oxazolines could be efficiently transformed intoβ-amino alcohol,which is an important moiety in pharmaceuticals.展开更多
文摘Ketoesters were successfully utilized as the bifunctionalization reagents to react with diaryl alkynes under visible light and photocatalyst or additives free conditions. A series of phenanthrenes containing acyl and ester groups were obtained in high yields. This protocol features with excellent regioselectivity, high efficiency, and atomic economy.
基金financially supported by the National Natural Science Foundation of China (No.21602046)the MOST of China (No.2016YFE0132600)the Doctor’s Scientific Research Foundation of Henan University of Chinese Medicine (No.BSJJ2016-12)
文摘The visible light promoted C-H sulfonylmethylation of imidazopyridines with easily accessible bromomethyl sulfones under mild reaction conditions was described.This protocol provides an effective and practical access to sulfonylmethylated imidazopyridines with good functional group tolerance.The desired products were provided in moderate to excellent yields for 50 examples at room temperature.The method could also be an attractive strategy to install a methyl group on imidazopyridines.
基金partial financial support from the Ministry of Science and Technology of China (No. 2016YFE0132600)Zhengzhou University
文摘Rhodium(Ⅲ)-catalyzed synthesis of indole derivatives has been realized via cascade reaction of C -H alkylation/nucleophilic cyclization starting from readily available N-phenylpyridin-2-amines and sulfoxonium ylides. Notably, this transformation could smoothly proceed with high yields, good regioselectivity, and feature broad group tolerance and under redox-neutral condition to avoid external oxidant. The titled products are potentially important building blocks in the organic synthesis through various chemical transformations.
基金partial financial support from the Ministry of Science and Technology of China(No.2016YFE0132600)Zhengzhou University。
文摘A selective ring-opening [3+2] cyclization reaction of benzo[d]isoxazoles with 2-bromo-propanamides has been developed.The azaoxyallyl cation intermediates are employed as C^O 3-atom synthon to build oxa-heterocycles via the selectivity of suitable cyclization partners.This transformation provides rapid access to highly functionalized 2-hydroxyaryl-oxazolines under mild conditions and excellent regioselectivity.
基金financial support from the National Natural Science Foundation of China (No.21801087)Fundamental Research Funds for the Central Universities CCNU (No.CCNU19QN064)+2 种基金the Ministry of Science and Technology of China (No.2016YFE0132600)Henan Center for Outstanding Overseas Scientists (No.GZS2020001)the Key Scientific and Technological Project of Henan Province (No.212102311068)。
文摘Anthrones are key structural motifs in many natural products, bioactive compounds and pharmaceutical chemicals. Earth-abundant-metal-catalyzed asymmetric functionalization of anthrones has not proved to be viable. Herein, we disclosed a highly enantioselective propargylic substitution of anthrones with propargylic esters using copper salts with chiral N, N, P-ligand. This strategy is amenable to a broad range of substrates, uses readily available starting materials, provides excellent yields with remarkable enantioselectivity under mild conditions, and enables attractive products diversification routes.
基金financial support from the Ministry of Science and Technology of China (No.2016YFE0132600)Henan Center for Outstanding Overseas Scientists (No.GZS2020001)Zhengzhou University。
文摘A novel approach for the synthesis of 4-aminoquinazolines has been developed via rhodium(Ⅲ)-catalyzed [4+2] annulation of N-arylbenzamidines with 1,4,2-dioxazol-5-ones.This reaction features excellent regioselectivity,broad substrate scope and high step economy,which would provide the refe rence for the construction of the fused 4-aminoquinazolines with biologically and pharmacologically active compounds.
基金financial support from the Ministry of Science and Technology of China (No.2016YFE0132600)Henan Center for Outstanding Overseas Scientists (No. GZS2020001)+1 种基金National Innovation and Entrepreneurship Training Program for College students (No.201910459064)Zhengzhou University
文摘A green tandem reaction,including insertion/aerobic oxidation/bisindolylation,starting from indoles and diazo compounds has been developed.The combination of water and fluorinated alcohol plays dual roles as solvent and promoter in this chemical transformation.Molecular oxygen in the air acts as an oxidant.3,3’-Bis(indolyl)methanes with quaternary carbon were produced under metal-free conditions.No any catalyst and additive were required.N2 and water were released as sole by-products.Absence of water and fluorinated alcohol resulted in Wolff rearrangement product.
基金supported by the National Natural Science Foundation of China(No.21572072)111 Project(No.BC2018061)+1 种基金the financial support of Scientific Research Foundation of Xiamen Huaxia University(No.HX201807)Outstanding Youth Scientific Research Cultivation Plan in Fujian Province University(No.201808)。
文摘A ferrocene-initiated radical reaction of benzoquinone with amines has been successfully developed for the direct access to diaminobenzoquinone imines in high yields,in which the comme rcially available and cheap ferrocene was employed as a radical initiator and TBHP was used as an oxidant.Moreover,this reaction could be achieved with low loading of ferrocene(0.5 mol%).This protocol is highly efficient with good substrate tolera nce and provides a new approach for the construction of benzoquinone imines with potential pharmaceutical interest.
基金the financial support from the National Natural Science Foundation of China(Nos.21572072 and 21602064)111 Project(No.BC2018061)。
文摘As balanced electron-rich P,C-chelating ligands,phosphine-phosphonium-ylides are considered for their ability to in situ promote palladium-catalysed direct C(sp^2)—H arylation.Using methyl phosphonium salts of 2,2’-bis(diphenylphosphino)-1,1’-binaphtyl("methyl-BINAPIUM")as ylide precursors under optimized reaction conditions,arylation of benzoxazole was found to proceed in moderate to high yield to give functional 2-aryl benzoxazoles.A strong anion effect of the non-salt free ylide was evidenced(TfO^->I^->PF6^-≈salt-free).This first example of phosphonium ylides as ligands in catalytic C-H activation extends the prospect of their general implementation in homogeneous transition metal catalysis.
基金partial financial support from the National Key R&D Program of China(No.2016YFE0132600)Henan Center for Outstanding Overseas Scientists(No.GZS2020001)Key Scientific and Technological Project of Henan Province(No.212102311068)。
文摘A Ru(Ⅲ)-catalyzed annulation reaction of 2-aminoaromatic aldehydes(ketones)and isoxazoles to afford diverse 3-cyanoquinolines has been developed.Notably,isoxazole acted as a cyclization reagent and nontoxic cyano source via N-O bond cleavage and fragmentation.Variously substituted(especially 6-or 7-substituted)quinolines could be easily afforded.This procedure features wide functional group compatibility,efficiency and avoiding toxic cyano source.Meanwhile,this protocol could be successfully applied to scale-up synthesis.Further chemical transformations of 3-cyanoquinoline could give some valuable skeletons,demonstrating its potential in synthetic application.
基金This work was supported by the National Natural Science Foundation of China(No.21572072)111 Project(No.BC 2018061)Xiamen Southern Oceanographic Center(No.15PYY052SF01).
文摘Rhodium(Ⅲ)-catalyzed[4+1]cyclization of azobenzenes with α-Cl ketones has been developed.3-Acyl-2H-indazoles could be easily afforded in up to 97%yields for more than 30 examples.The obtained products are potentially valuable in organic synthesis and drug discovery.This protocol featured with high efficiency,extensive functional group tolerance and mild reaction conditions.The one-step efficient construction of an anti-inflammatory agent confirms the practicability of this procedure.
基金the Ministry of Science and Technology of China(No.2016YFE0132600)Henan Center for Outstanding Overseas Scientists(No.GZS2020001)。
文摘Cp^*Co(Ⅲ)-catalyzed direct C—H amidation of azines has been developed.This co nversion could proceed smoothly in the absence of external oxidants,acids or bases,with excellent regioselectivity and broad functional group tolerance,CO2 was released as the sole byproduct,thus providing an environmentally benign amidation process.The products obtained are important intermediates in organic synthesis.
基金the National Natural Science Foundation of China(No.21572072)111 Project(No.BC2018061)and Y.Feng thanks the financial support of Scientific Research Foundation of Xiamen Huaxia University(No.HX201807)+1 种基金Outstanding Youth Scientific Research Cultivation Plan in Fujian Province University(No.201808)the Fujian Education and Scientific Research Project for Young and Middle-aged Teachers(No.JAT190990)。
文摘Pd-catalyzed oxidative homocoupling of 2-arylquinazolinones was successfully developed for the direct construction of biaryls via C—H bond activation.New well-defined structure that possessed two quinazolinone units was obtained with high efficiency and atomic economy.The protocols offer an efficient approach to the synthetically useful and functionalized biaryls in good yields using quinazolinone as a directing group.
基金supported by the National Natural Science Foundation of China (No.21572072)Xiamen Southern Oceanographic Center (No.15PYY052SF01)+3 种基金111 Project (No.BC2018061)the Postgraduates Innovative Fund in Scientific Research of Huaqiao Universitythe financial support of Scientific Research Foundation of Xiamen Huaxia University (No. HX201807)Outstanding Youth Scientific Research Cultivation Plan in Fujian Province University (2018)
文摘An Ir-catalyzed selective mono-sulfamidation of 2-arylquinazolinones has been achieved with a low catalyst loading under mild conditions.A series of regioselective mono-sulfamided 2-arylquinazolinones were obtained in up to 90%yields.Compared with our previous work of constructing di-sulfamidated 2-arylquinazolinones,the mono-sulfamided products could be obtained selectively by changing the ratio of substrates,the loading of catalyst,acid additive,and reaction time.
基金supported by the National Natural Science Foundation of China (Nos. 21602064 and 21572072)the Natural Science Foundation of Fujian Province (No. 2015J01056)Huaqiao University (No. ZQN-PY317)
文摘We herein report a highly regioselective rhodium-catalyzed C6-and C7—H bond functionalization of indolines with alkynes by using 2-pyrimidine as a directing group. Moreover, NH-free benzo[g]indole unit could be obtained by an oxidation/removal of the directing group sequence.
文摘In 1998.Paul Anastas and John Warner defined 12 Principles of Green Chemistry,aiming at cleaner processes,safer products and increasing use of renewable rather than fossil resources.With the growing awareness of environmental issues,the international chemical community is driven to develop novel and environmentally friendly synthetic strategies for the replacement of inefficient and pollutional chemical processes.Delightedly,a lot of eco-friendly synthetic methodologies have been established over the past decades.
基金We acknowledge partial financial support from the Ministry of Science and Technology of China(No.2016YFE0132600)Henan Center for Outstanding Overseas Scientists(No.GZS2020001)and Zhengzhou University。
文摘A visible-light-promoted formal[2+2+1]cyclization of N-aryl glycines with quinoxalin-2(1H)-ones to synthesize tetrahydroimidazo[1,5-a]quinoxalin-4(5H)-ones have been developed.The protocol features operational simplicity,mild reaction conditions with blue LED light employing Ru(bpy)3Cl2.6H2O as a photoredox catalyst,a combination of O2 from air and Cu(OAc)2 as the oxidant and broad substrate applicability.
文摘Due to using （R）- or （S）-a-methylbenzylamine as a chiral auxiliary, and low-temperature regime for reduction of the intermediate ferrocenyl-mono- or 1,1＇-bis-ketimines, the corresponding secondary mono- or 1,1＇-bis-amines were prepared with high diastereoselectivity. Removal of the a-methylbenzyl group afforded the optically active primary mono- and bis-ferrocenylethylamines in high yields. The absolute configuration of （R,R）-3a and （S,S）-3b was determined by X-ray single crystal diffraction.
基金supported by the NSF of China(21572072)Xiamen Southern Oceanographic Center(15PYY052SF01)111 Project(BC2018061).
文摘Photoredox-catalyzed generation of sulfonated oxazolines starting from N-allylamides,DABCO·(SO2)2,and aryldiazonium salts has been developed.A range of sulfonated oxazolines were obtained in moderate to good yields.This transformation involves the sequential insertion of sulfur dioxide,intermolecular sulfonylation of alkenes and intramolecular cyclization via a radical process.This protocol features good compatibility of functional groups and mild reaction conditions.Sulfonated oxazolines could be efficiently transformed intoβ-amino alcohol,which is an important moiety in pharmaceuticals.
