Accelerated Ru–Cu Trinuclear Cooperative C−H Bond Functionalization of Carbazoles: A Kinetic and Computational Investigation

Abstract

The mechanism of a trinuclear cooperative dehydrogenative C−N bond-forming reaction is investigated in this work, which avoids the use of chelate-assisting directing groups. Two new highly efficient Ru/Cu co-catalyzed systems were identified, allowing orders of magnitude greater TOFs than the previous state of the art. In-depth kinetic studies were performed in combination with advanced DFT calculations, which reveal a decisive rate-determining trinuclear Ru–Cu cooperative reductive elimination step (CRE).