Visible light promoted difunctionalization of alkynes is reviewed. The difunctionalization reaction is achieved by different reagents. Radicals such as carbon(sp3), carbon(sp2), and other heteroatom(P, S, N, Se, O, an...Visible light promoted difunctionalization of alkynes is reviewed. The difunctionalization reaction is achieved by different reagents. Radicals such as carbon(sp3), carbon(sp2), and other heteroatom(P, S, N, Se, O, and halide) radicals initiated by visible light can undergo radical addition to a carbon-carbon triple bond. Upon further transformation, the desired difunctionalized products are obtained. Some organometallic complexes can be activated by visible light;the difunctionalization of alkynes is catalyzed by these species. Other reagents like 1,3-dipole precursors could also react with alkynes to give difunctionalization products;here, the 1,3-dipole derivatives are obtained by visible light photocatalysis. So far, the strategy has been succeeded in the formation of C–C bonds and C–X bonds. Several valuable chemical skeletons have been constructed under mild conditions. However, high regio-and stereoselectivities in some direct difunctionalization methodologies are yet to be achieved.展开更多
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
A photoredox-catalyzed cascade carbon/carboxylation of activated alkenes with malonates acetals and CO_(2) has been achieved,leading to a range of functionalized 1,1,3-tricarboxylates in good efficiency under mild rea...A photoredox-catalyzed cascade carbon/carboxylation of activated alkenes with malonates acetals and CO_(2) has been achieved,leading to a range of functionalized 1,1,3-tricarboxylates in good efficiency under mild reaction conditions.This reaction provides a facile and sustainable method for the synthesis of tricarboxylates by using CO_(2) as the carboxylic source.展开更多
基金supported by Zhejiang Provincial Natural Science Foundation of China(LR19B020001)the National Natural Science Foundation of China(21472162,21772171)the National Basic Research Program of China(2015CB856600)~~
文摘Visible light promoted difunctionalization of alkynes is reviewed. The difunctionalization reaction is achieved by different reagents. Radicals such as carbon(sp3), carbon(sp2), and other heteroatom(P, S, N, Se, O, and halide) radicals initiated by visible light can undergo radical addition to a carbon-carbon triple bond. Upon further transformation, the desired difunctionalized products are obtained. Some organometallic complexes can be activated by visible light;the difunctionalization of alkynes is catalyzed by these species. Other reagents like 1,3-dipole precursors could also react with alkynes to give difunctionalization products;here, the 1,3-dipole derivatives are obtained by visible light photocatalysis. So far, the strategy has been succeeded in the formation of C–C bonds and C–X bonds. Several valuable chemical skeletons have been constructed under mild conditions. However, high regio-and stereoselectivities in some direct difunctionalization methodologies are yet to be achieved.
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.
文摘A photoredox-catalyzed cascade carbon/carboxylation of activated alkenes with malonates acetals and CO_(2) has been achieved,leading to a range of functionalized 1,1,3-tricarboxylates in good efficiency under mild reaction conditions.This reaction provides a facile and sustainable method for the synthesis of tricarboxylates by using CO_(2) as the carboxylic source.
基金supported by the 973 Program of China(No.2009CB825300)the National Natural Science Foundation of China(Nos.20972175,20923005)the Science and Technology Commission of the Shanghai Municipality(No.11JC1415000)~~
