Reactivities of α‐Oxo BMIDA Gold Carbenes Generated by Gold‐Catalyzed Oxidation of BMIDA‐Terminated Alkynes

Abstract An oxidative strategy is reported to access α‐oxo BMIDA gold carbenes directly from BMIDA‐terminated alkynes. Besides offering expedient access to seldom studied boryl metal carbenes, these BMIDA gold carbene species undergo facile insertions into methyl, methylene, methine, and benzylic C−H bonds in the absence of the Thorpe–Ingold effect. They also undergo efficient OH insertion, cyclopropanation, and F−C alkylations. This chemistry provides rapid access to structurally diverse α‐BMIDA ketones, which are scarcely documented. In combination with DFT studies, the role of BMIDA is established to be an electron‐donating group that attenuates the high electrophilicity of the gold carbene center.