Visible light‐driven carboxylation with CO_(2) have emerged as a sustainable and powerful way to transfer waste to treasure.However,it is still challenging for aryl fluorides due to the low reactivities of both C(sp2...Visible light‐driven carboxylation with CO_(2) have emerged as a sustainable and powerful way to transfer waste to treasure.However,it is still challenging for aryl fluorides due to the low reactivities of both C(sp2)−F bonds and CO_(2).Herein,we report the first photocatalytic carboxylation of aryl C−F bonds with CO_(2).The visible‐light photoredox catalysis enables selective carboxylation of strong C(sp2)−F bonds in diverse polyluoroarenes,such as penta‐,tetra‐,and tri‐fluoroarenes under mild conditions,providing a facile access to a series of important polyfluoroaryl carboxylic acids with good yields.In contrast to previous reports of direct capture of polyfluoroaryl radicals,mechanistic studies suggest that the reduction of fleeting polyfluoroaryl radicals into polyfluoroaryl anions might be involved in this transformation,which may open a new avenue for photocatalytic functionalization of aryl C−F bonds.展开更多
An effective method for Pd-catalyzed cross-coupling between polyfluoroarenes and cyclic vinyl triflates has been developed.This protocol provides a useful and facile access to polyfluoroarylated cyclic alkenes that ar...An effective method for Pd-catalyzed cross-coupling between polyfluoroarenes and cyclic vinyl triflates has been developed.This protocol provides a useful and facile access to polyfluoroarylated cyclic alkenes that are difficult to prepare otherwise.The advantages of this method are its high efficiency and operational simplicity.展开更多
Sulfonatocalix[4]arene lowers the critical aggregation concentration of fluorocarbon surfactant pronouncedly by a factor of ca.100 to form binary amphiphilic aggregates on the basis of host-guest complexation,which wa...Sulfonatocalix[4]arene lowers the critical aggregation concentration of fluorocarbon surfactant pronouncedly by a factor of ca.100 to form binary amphiphilic aggregates on the basis of host-guest complexation,which was identified by1H NMR spectroscopy,fluorescence spectroscopy,optical transmittance spectroscopy,dynamic laser scattering,high-resolution transmission electron microscopy,scanning electron microscopy,and surface tension experiments.Moreover,the resulting aggregates can respond to external stimuli,including temperature and inclusion of competitor guest.Therefore,the present system may have potential applications in drug delivery systems.展开更多
文摘Visible light‐driven carboxylation with CO_(2) have emerged as a sustainable and powerful way to transfer waste to treasure.However,it is still challenging for aryl fluorides due to the low reactivities of both C(sp2)−F bonds and CO_(2).Herein,we report the first photocatalytic carboxylation of aryl C−F bonds with CO_(2).The visible‐light photoredox catalysis enables selective carboxylation of strong C(sp2)−F bonds in diverse polyluoroarenes,such as penta‐,tetra‐,and tri‐fluoroarenes under mild conditions,providing a facile access to a series of important polyfluoroaryl carboxylic acids with good yields.In contrast to previous reports of direct capture of polyfluoroaryl radicals,mechanistic studies suggest that the reduction of fleeting polyfluoroaryl radicals into polyfluoroaryl anions might be involved in this transformation,which may open a new avenue for photocatalytic functionalization of aryl C−F bonds.
基金financially supported by the National Basic Research Program of China (973 Program,2012CB821600)the National Natural Science Foundation of China (21172242) thesupport of Shanghai institute of Organic Chemistry,the Chinese Academy of Sciences.
文摘An effective method for Pd-catalyzed cross-coupling between polyfluoroarenes and cyclic vinyl triflates has been developed.This protocol provides a useful and facile access to polyfluoroarylated cyclic alkenes that are difficult to prepare otherwise.The advantages of this method are its high efficiency and operational simplicity.
基金supported by the National Basic Research Program of China(2011CB932502)the National Natural Science Foundation of China(91227107 and 21172119)
文摘Sulfonatocalix[4]arene lowers the critical aggregation concentration of fluorocarbon surfactant pronouncedly by a factor of ca.100 to form binary amphiphilic aggregates on the basis of host-guest complexation,which was identified by1H NMR spectroscopy,fluorescence spectroscopy,optical transmittance spectroscopy,dynamic laser scattering,high-resolution transmission electron microscopy,scanning electron microscopy,and surface tension experiments.Moreover,the resulting aggregates can respond to external stimuli,including temperature and inclusion of competitor guest.Therefore,the present system may have potential applications in drug delivery systems.