Abstract
Developing applicable methods to forge linkages between sp3 and sp2-hydridized carbons is of great sig-nificance in drug discovery.We show here a new,Ni-catalyzed reductive cross-coupling reaction that forms Csp3-Csp2 bonds from aryl iodides and cyclic sulfonium salts.Notably,Csp3-Csp2 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 compu-tational mechanistic studies support LNiIAr as an active species,while the untraditional anti-Markovnikov selective alkylation of asymmetric sulfonium salts is determined by the oxidative S-substitution of sul-fonium salts with LNiIAr.This protocol further expands the range of alkyl electrophiles under the CRCC conditions and provides a new strategy for the construction of Csp3-Csp2 bonds.