Although,great achievements have been made in the synthesis of heterocycles using radical addition/cyclization strategy,developing versatile alkyl radical precursors,especially the non-stabilized long chain alkyl radi...Although,great achievements have been made in the synthesis of heterocycles using radical addition/cyclization strategy,developing versatile alkyl radical precursors,especially the non-stabilized long chain alkyl radicals for this strategy still remains a huge challenge.Herein,we report an efficient annulation cascade reaction between cyclosulfonium salts and alkenes for the synthesis of sulfur-containing N-heterocycles by visible light/copper catalysis under mild conditions.The C—S bond cleavage/radical cascade reaction delivers a variety of corresponding N-heterocycles containing aryl alkyl thioether motifs with good functional group tolerance.Significantly,the current system could be used for the late-stage functionalization of complex bioactive molecules.展开更多
A photocatalyst-free visible-light-promoted three-component reaction of thianthrenium salts,isothiocyanates,and amines is presented,which affords a rapid and efficient approach to S-arylisothioureas under mild conditi...A photocatalyst-free visible-light-promoted three-component reaction of thianthrenium salts,isothiocyanates,and amines is presented,which affords a rapid and efficient approach to S-arylisothioureas under mild conditions.This developed method exhibits the advantages of readily available raw materials,broad substrate scope,good functional tolerance,and operational simplicity.It is worth mentioning that the byproduct thianthrene can be recycled in quantity,ultimately maximizing the atomic economy of the reaction and avoiding chemical waste.Mechanism investigations support the strategy involving a photoinduced EDA complex.展开更多
An eco-friendly and convenient method is developed herein for the synthesis of S-aryl dithiocarbamates via visible-light-induced SET process of an EDA complex between thianthrenium salt functionalized arenes and dithi...An eco-friendly and convenient method is developed herein for the synthesis of S-aryl dithiocarbamates via visible-light-induced SET process of an EDA complex between thianthrenium salt functionalized arenes and dithiocarbamate anions under mild aqueous micellar conditions.This strategy indirectly realizes the method for constructing S-aryl dithiocarbamates through site-selective C−H functionalization of arenes.Most importantly,the reaction proceeded smoothly without addition of any photocatalyst,and the by-product thianthrene is recycled in quantity,ultimately minimizing the production of chemical waste.This protocol provides a promising synthesis candidate for the construction of valuable S-aryl dithiocarbamates,which also opens up a new avenue for micellar photocatalysis.展开更多
Transition-metal-catalyzed decarboxylative and C–H functionalization strategy for the construction of Csp^(2)-Csp^(2),Csp^(2)-Csp,and Csp^(2)-Csp^(3) bonds has been extensively studied.However,research surveys of thi...Transition-metal-catalyzed decarboxylative and C–H functionalization strategy for the construction of Csp^(2)-Csp^(2),Csp^(2)-Csp,and Csp^(2)-Csp^(3) bonds has been extensively studied.However,research surveys of this synthetic strategy for the Csp^(3)-Csp^(3) bond forming reactions are surprisingly scarce.Herein,we present an efficient approach for the rapid formation of Csp^(3)–Csp^(3) bond through copper-catalyzed decarboxylative Csp^(3)–H functionalization.The present method should provide a useful access to C3-substituted indole scaffolds with possible biological activities.Mechanistic experiments and DFT calculations supported a dual-Cu(Ⅱ)-catalytic cycle involving rate-determining decarboxylation in an outer-sphere radical pathway and spin-crossover-promoted C–C bond formation.This strategy offers a promising synthesis method for the construction of Csp^(3)–Csp^(3) bond in the field of synthetic and pharmaceutical chemistry and extends the number of still limited copper-catalyzed decarboxylative Csp^(3)–Csp^(3) bond forming reaction.展开更多
基金the National Natural Science Foundation of China(22271170)the Scientific Research Foundation of Qingdao University of Science and Technology.
文摘Although,great achievements have been made in the synthesis of heterocycles using radical addition/cyclization strategy,developing versatile alkyl radical precursors,especially the non-stabilized long chain alkyl radicals for this strategy still remains a huge challenge.Herein,we report an efficient annulation cascade reaction between cyclosulfonium salts and alkenes for the synthesis of sulfur-containing N-heterocycles by visible light/copper catalysis under mild conditions.The C—S bond cleavage/radical cascade reaction delivers a variety of corresponding N-heterocycles containing aryl alkyl thioether motifs with good functional group tolerance.Significantly,the current system could be used for the late-stage functionalization of complex bioactive molecules.
基金supported by the National Natural Science Foundation of China(No.22271170)the Scientific Research Foundation of Qingdao University of Science and Technology。
文摘A photocatalyst-free visible-light-promoted three-component reaction of thianthrenium salts,isothiocyanates,and amines is presented,which affords a rapid and efficient approach to S-arylisothioureas under mild conditions.This developed method exhibits the advantages of readily available raw materials,broad substrate scope,good functional tolerance,and operational simplicity.It is worth mentioning that the byproduct thianthrene can be recycled in quantity,ultimately maximizing the atomic economy of the reaction and avoiding chemical waste.Mechanism investigations support the strategy involving a photoinduced EDA complex.
基金supported by the National Natural Science Foundation of China(No.22271170)the Scientific Research Foundation of Qingdao University of Science and Technology。
文摘An eco-friendly and convenient method is developed herein for the synthesis of S-aryl dithiocarbamates via visible-light-induced SET process of an EDA complex between thianthrenium salt functionalized arenes and dithiocarbamate anions under mild aqueous micellar conditions.This strategy indirectly realizes the method for constructing S-aryl dithiocarbamates through site-selective C−H functionalization of arenes.Most importantly,the reaction proceeded smoothly without addition of any photocatalyst,and the by-product thianthrene is recycled in quantity,ultimately minimizing the production of chemical waste.This protocol provides a promising synthesis candidate for the construction of valuable S-aryl dithiocarbamates,which also opens up a new avenue for micellar photocatalysis.
基金supported by the National Natural Science Foundation of China(No.21702119)Natural Science Foundation of Shandong Province(Nos.ZR2016JL012,ZR2020JQ07)the Scientific Research Foundation of Qingdao University of Science and Technology(No.1203043003457)。
文摘Transition-metal-catalyzed decarboxylative and C–H functionalization strategy for the construction of Csp^(2)-Csp^(2),Csp^(2)-Csp,and Csp^(2)-Csp^(3) bonds has been extensively studied.However,research surveys of this synthetic strategy for the Csp^(3)-Csp^(3) bond forming reactions are surprisingly scarce.Herein,we present an efficient approach for the rapid formation of Csp^(3)–Csp^(3) bond through copper-catalyzed decarboxylative Csp^(3)–H functionalization.The present method should provide a useful access to C3-substituted indole scaffolds with possible biological activities.Mechanistic experiments and DFT calculations supported a dual-Cu(Ⅱ)-catalytic cycle involving rate-determining decarboxylation in an outer-sphere radical pathway and spin-crossover-promoted C–C bond formation.This strategy offers a promising synthesis method for the construction of Csp^(3)–Csp^(3) bond in the field of synthetic and pharmaceutical chemistry and extends the number of still limited copper-catalyzed decarboxylative Csp^(3)–Csp^(3) bond forming reaction.
