Nickel-catalyzed cross-coupling reaction of carbamates with silylmagnesium reagents

The C-O bonds are kinetically inert in cross-coupling reactions compared to those of carbon-halogen bonds. Thus, developing methodologies for the activation of C-O bonds in cross-coupling reactions remains a major challenge. We disclose an unprecedented nickel mediated cross-coupling of carbamates with silylmagnesium reagents that does not require the expensive silylboranes. Silylmagnesium reagents were prepared from either silyllithium or silyl iodides. This methodology is distinguished by the synthesis of trimethylsilyl coupled product and its synthetic applications. Kinetic studies and radical clock experiments revealed the rate-limiting C-O bond cleavage, half order with respect to the catalyst and a non-radical transition state. (C) 2019 Elsevier Inc. All rights reserved.