A new Rh(Ⅲ)-catalyzed aldehydic C-H activation/[4+3]annulation cascade of N-sulfonyl-2-aminobenzaldehydes with gem-difluorocyclopropenes is reported for the first time,and used to produce a range of hitherto unreport...A new Rh(Ⅲ)-catalyzed aldehydic C-H activation/[4+3]annulation cascade of N-sulfonyl-2-aminobenzaldehydes with gem-difluorocyclopropenes is reported for the first time,and used to produce a range of hitherto unreported precedentedβ-monofluorinated benzo[b]azepin-5-ones with good yields and complete regioselectivity.This approach features a broad substrate scope,good functional group tolerance,and high regioselectivity,which may include Rh(Ⅲ)-catalyzed aldehydic C-H activation,tandem site-/regioselective insertion,defluorinated ring-scission,and 1,2-elimination.展开更多
Chloroalkanes are important building blocks in the synthesis,but their use in redox chemistry is limited by their negative reduction potentials.Electrosynthesis can precisely control the reaction energy just by adjust...Chloroalkanes are important building blocks in the synthesis,but their use in redox chemistry is limited by their negative reduction potentials.Electrosynthesis can precisely control the reaction energy just by adjusting the current or voltage to achieve the selectivity of regulation.In this study,the consecutively paired electrolyticmediated controllable radical cross-coupling of thiophenols with dichloromethane was developed to deliver the dithioacetals,sulfides,and sulfoxides in the absence of electrochemical mediator conditions.It features broad substrate scope,simple operation,gram-scale synthesis,and is eco-friendly.Mechanistic studies reveal that this electrochemical reaction is radical-induced cross-coupling of thiophenols with dichloromethane.展开更多
基金financial support from the schoollevel research projects of Yancheng Institute of Technology(No.xjr2020044)the National Natural Science Foundation of China(Nos.22101151 and 21971090)。
文摘A new Rh(Ⅲ)-catalyzed aldehydic C-H activation/[4+3]annulation cascade of N-sulfonyl-2-aminobenzaldehydes with gem-difluorocyclopropenes is reported for the first time,and used to produce a range of hitherto unreported precedentedβ-monofluorinated benzo[b]azepin-5-ones with good yields and complete regioselectivity.This approach features a broad substrate scope,good functional group tolerance,and high regioselectivity,which may include Rh(Ⅲ)-catalyzed aldehydic C-H activation,tandem site-/regioselective insertion,defluorinated ring-scission,and 1,2-elimination.
基金This work is supported by the National Natural Science Foundation of China(No.21902083)the Natural Science Foundation of Shandong Province(No.ZR2020QB130)This work is also supported by the Talent Program Foundation of Qufu Normal University(Nos.6132 and 6125).
文摘Chloroalkanes are important building blocks in the synthesis,but their use in redox chemistry is limited by their negative reduction potentials.Electrosynthesis can precisely control the reaction energy just by adjusting the current or voltage to achieve the selectivity of regulation.In this study,the consecutively paired electrolyticmediated controllable radical cross-coupling of thiophenols with dichloromethane was developed to deliver the dithioacetals,sulfides,and sulfoxides in the absence of electrochemical mediator conditions.It features broad substrate scope,simple operation,gram-scale synthesis,and is eco-friendly.Mechanistic studies reveal that this electrochemical reaction is radical-induced cross-coupling of thiophenols with dichloromethane.
