The first catalytic enantioselective C(sp)-C(sp^3) cross-coupling reaction between N-tosylhydrazones and trialkylsilylethynes in the presence of Cu(I) salts and chiral phosphoramidite ligands was developed. A se...The first catalytic enantioselective C(sp)-C(sp^3) cross-coupling reaction between N-tosylhydrazones and trialkylsilylethynes in the presence of Cu(I) salts and chiral phosphoramidite ligands was developed. A series of svnthetically interesting, functionalized alkynes were obtained with moderate to good enanttiselectivities (up to 83% ee). Cu(ll) carbene migratory insertion is proposed to be the enantio-determining step. KEYWORDS C(sp)--C(sp^3) cross-coupling, metal carbene, asymmetric catalysis, Cu(I) catalysts, N-tosylhydrazones展开更多
Herein,we report the first electrochemical strategy for the borylation of aryl iodides via a radical pathway using current as a driving force.A mild reaction condition allows an assorted range of readily available ary...Herein,we report the first electrochemical strategy for the borylation of aryl iodides via a radical pathway using current as a driving force.A mild reaction condition allows an assorted range of readily available aryl iodides to be proficiently converted into synthetically valuable arylboronic esters under transition metal catalyst-free conditions.Moreover,this method also shows good functional group tolerance.Initial control mechanistic experiments reveal the formation of aryl radical as a key intermediate and the current plays an important role in the generation of radical intermediate.展开更多
基金Acknowledgement The project is supported by the National Basic Research Program of China (973 Program, No. 2015CB856600), the National Natural Science Foundation of China (Grant 21472004, 21332002) and the China Postdoctoral Science Foundation Funded Project (2015M5B0911).
文摘The first catalytic enantioselective C(sp)-C(sp^3) cross-coupling reaction between N-tosylhydrazones and trialkylsilylethynes in the presence of Cu(I) salts and chiral phosphoramidite ligands was developed. A series of svnthetically interesting, functionalized alkynes were obtained with moderate to good enanttiselectivities (up to 83% ee). Cu(ll) carbene migratory insertion is proposed to be the enantio-determining step. KEYWORDS C(sp)--C(sp^3) cross-coupling, metal carbene, asymmetric catalysis, Cu(I) catalysts, N-tosylhydrazones
基金the National Natural Science Foundation of China(Grant No.21772003).
文摘Herein,we report the first electrochemical strategy for the borylation of aryl iodides via a radical pathway using current as a driving force.A mild reaction condition allows an assorted range of readily available aryl iodides to be proficiently converted into synthetically valuable arylboronic esters under transition metal catalyst-free conditions.Moreover,this method also shows good functional group tolerance.Initial control mechanistic experiments reveal the formation of aryl radical as a key intermediate and the current plays an important role in the generation of radical intermediate.