Developing applicable methods to forge linkages between sp^(3)and sp^(2)-hydridized carbons is of great significance in drug discovery.We show here a new,Ni-catalyzed reductive cross-coupling reaction that forms Csp^(...Developing applicable methods to forge linkages between sp^(3)and sp^(2)-hydridized carbons is of great significance in drug discovery.We show here a new,Ni-catalyzed reductive cross-coupling reaction that forms Csp^(3)-Csp^(2)bonds from aryl iodides and cyclic sulfonium salts.Notably,Csp^(3)-Csp^(2)bonds can be forged selectively at the iodine-bearing carbon of bromo(iodo)arenes which is usually recognized as a huge challenge under the catalytic reductive cross-coupling(CRCC)conditions.Experimental and computational mechanistic studies support LNi~IAr as an active species,while the untraditional anti-Markovnikov selective alkylation of asymmetric sulfonium salts is determined by the oxidative S-substitution of sulfonium salts with LNi~IAr.This protocol further expands the range of alkyl electrophiles under the CRCC conditions and provides a new strategy for the construction of Csp^(3)-Csp^(2)bonds.展开更多
基金supported by the National Natural Science Foundation of China(No.22271170)the Scientific Research Foundation of Qingdao University of Science and Technology。
文摘Developing applicable methods to forge linkages between sp^(3)and sp^(2)-hydridized carbons is of great significance in drug discovery.We show here a new,Ni-catalyzed reductive cross-coupling reaction that forms Csp^(3)-Csp^(2)bonds from aryl iodides and cyclic sulfonium salts.Notably,Csp^(3)-Csp^(2)bonds can be forged selectively at the iodine-bearing carbon of bromo(iodo)arenes which is usually recognized as a huge challenge under the catalytic reductive cross-coupling(CRCC)conditions.Experimental and computational mechanistic studies support LNi~IAr as an active species,while the untraditional anti-Markovnikov selective alkylation of asymmetric sulfonium salts is determined by the oxidative S-substitution of sulfonium salts with LNi~IAr.This protocol further expands the range of alkyl electrophiles under the CRCC conditions and provides a new strategy for the construction of Csp^(3)-Csp^(2)bonds.
