Cobalt-Catalyzed Carbonylative Conversion of Unactivated Alkyl Chlorides

Unactivated alkyl chlorides are ideal but underutilized building blocks in carbonylation due to the high strength of C-Cl bonds and the limitations of existing transition-metal catalysis. Herein, we describe a Salen-cobalt-catalyzed carbonylative transformation of unactivated alkyl chlorides under mild conditions, enabled by the supernucleophilic Co(I) center that efficiently promotes S_N2-type C-Cl activation. This system accommodates sterically hindered nucleophiles and proceeds through a well-supported radical-involved organocobalt catalytic cycle, providing a general platform for carbonylation of challenging alkyl chlorides.