The radical addition/functional group migration strategy has emerged as a powerful tool for the difunctionalization of unsaturated hydrocarbons,yet the heteroatom-mediated functional group migration remains largely un...The radical addition/functional group migration strategy has emerged as a powerful tool for the difunctionalization of unsaturated hydrocarbons,yet the heteroatom-mediated functional group migration remains largely unexplored.Herein,we report an unprecedented radical difunctionalization of alkynes employing oxime esters as bifunctional reagents through a novel C-centered radical addition/N-centered radical translocation sequence.This innovative transformation paradigm enables efficient alkylamination of alkynes under mild photocatalytic redox conditions.Mechanistic investigations reveal a cascade sequence initiated by single-electron transfer from oxime derivatives,proceeding through radical addition,6-exo-trig cyclization,and subsequent imino group migration.展开更多
Alkylamines play an important role in medicinal chemistry,while carboxylic acids are commonly found in many natural products and pharmaceuticals.In this study,we developed a direct photoredox-catalyzed decarboxylative...Alkylamines play an important role in medicinal chemistry,while carboxylic acids are commonly found in many natural products and pharmaceuticals.In this study,we developed a direct photoredox-catalyzed decarboxylative amination of alkyl carboxylic acids using a novel N-centered radical scavenger.This method avoids pre-activation and transition-metal catalysts,allowing a diverse range of readily available carboxylic acids to be efficiently converted into medicinally valuable amines.Further mechanistic studies and DFT calculations were conducted to provide evidence for the proposed photoredox-catalyzed pathway.This protocol is operationally simple and has excellent functional group compatibility,which is likely to be of great use in synthetic chemistry.展开更多
During the past few years, with the rapid development of mild methods for the generation of radical species, great progress in radical cascade reactions of unsaturated C–C bonds has been made. Many radical cascade re...During the past few years, with the rapid development of mild methods for the generation of radical species, great progress in radical cascade reactions of unsaturated C–C bonds has been made. Many radical cascade reactions involve functional groups migration, which leads structurally much more diverse, complex and valuable compounds not easily obtained through other methods. In this review, the recent achievements in unsaturated C–C bonds radical cascade reactions involving migration are summarized.展开更多
A green and straightforward electrosynthesis of substituted indoles has been developed through dehydration and intramolecular dehydrogenative C–N bond-forming radical cross-coupling from 1-(2-aminophenyl)alcohols und...A green and straightforward electrosynthesis of substituted indoles has been developed through dehydration and intramolecular dehydrogenative C–N bond-forming radical cross-coupling from 1-(2-aminophenyl)alcohols under metal,iodine and oxidant-free conditions.This electrochemical indole synthesis strategy has an excellent functional group,water and air tolerance.And,a possible cyclization process was proposed based on the radicaltrapping,intermediate verification,cyclic voltammetry,EPR and control experiments.展开更多
基金supported by the Shaanxi Provincial Natural Science Basic Research Plan(2025JC-YBMS-114)the National Key Research and Development Program of China(2024YFB3212500)+1 种基金the Xi’an Jiaotong University(7121192002)the Fundamental Research Funds for the Central Universities(xzy022024023)。
文摘The radical addition/functional group migration strategy has emerged as a powerful tool for the difunctionalization of unsaturated hydrocarbons,yet the heteroatom-mediated functional group migration remains largely unexplored.Herein,we report an unprecedented radical difunctionalization of alkynes employing oxime esters as bifunctional reagents through a novel C-centered radical addition/N-centered radical translocation sequence.This innovative transformation paradigm enables efficient alkylamination of alkynes under mild photocatalytic redox conditions.Mechanistic investigations reveal a cascade sequence initiated by single-electron transfer from oxime derivatives,proceeding through radical addition,6-exo-trig cyclization,and subsequent imino group migration.
基金financial support from National Natural Science Foundation of China(NSFC),Youth program(Grant No.22101173)Fundamental Research Funds for the Central Universities(24X010301678)"Thousand Talents Plan,Youth project"and startup funding from Shanghai Jiao Tong University(SJTU).
文摘Alkylamines play an important role in medicinal chemistry,while carboxylic acids are commonly found in many natural products and pharmaceuticals.In this study,we developed a direct photoredox-catalyzed decarboxylative amination of alkyl carboxylic acids using a novel N-centered radical scavenger.This method avoids pre-activation and transition-metal catalysts,allowing a diverse range of readily available carboxylic acids to be efficiently converted into medicinally valuable amines.Further mechanistic studies and DFT calculations were conducted to provide evidence for the proposed photoredox-catalyzed pathway.This protocol is operationally simple and has excellent functional group compatibility,which is likely to be of great use in synthetic chemistry.
基金supported by the National Natural Science Foundation of China(21831002,21801039)Ten Thousand Talents Program,the Jilin Province Natural Science Foundation(20160519003JH)the Fundamental Research Funds for the Central Universities(2412018QD007)
文摘During the past few years, with the rapid development of mild methods for the generation of radical species, great progress in radical cascade reactions of unsaturated C–C bonds has been made. Many radical cascade reactions involve functional groups migration, which leads structurally much more diverse, complex and valuable compounds not easily obtained through other methods. In this review, the recent achievements in unsaturated C–C bonds radical cascade reactions involving migration are summarized.
基金The research was supported by the Natural Science Foundation of Jiangsu Province,Frontier Project(No.BK20212003)National Science Foundation of China(No.22008118).
文摘A green and straightforward electrosynthesis of substituted indoles has been developed through dehydration and intramolecular dehydrogenative C–N bond-forming radical cross-coupling from 1-(2-aminophenyl)alcohols under metal,iodine and oxidant-free conditions.This electrochemical indole synthesis strategy has an excellent functional group,water and air tolerance.And,a possible cyclization process was proposed based on the radicaltrapping,intermediate verification,cyclic voltammetry,EPR and control experiments.
