Inherent vs Apparent Chemoselectivity in the Kumada–Corriu Cross-Coupling Reaction

Abstract

The Kumada-Corriu reaction is a powerful tool for C-C bond formation, but is seldom utilized due to perceived chemoselectivity issues. Herein, we demonstrate that high-yielding couplings can occur in the presence of many electrophilic and heterocyclic functional groups. Our strategy is mechanically based, matching oxidative addition rates with the rate of syringe pump addition of the Grignard reagent. The mechanistic reason for the effectiveness of this strategy is uncovered by continuous-infusion ESI-MS studies.