Experimental and Computational Studies on Cp*CyRh(III)/KOPiv-Catalyzed Intramolecular Dehydrogenative Cross-Couplings
Liping Li1, Hui Gao1, Ming Sun1
1Guangzhou Municipal and Guangdong Provincial Key Laboratory of Protein Modification and Degradation & Molecular Target and Clinical Pharmacology, State Key Laboratory of Respiratory Disease, School of Pharmaceutical Sciences & the Fifth Affiliated Hospital, Guangzhou Medical University, Guangzhou, Guangdong 511436, China.
Abstract:
Described herein is an unusual Cp*CyRh(III)-catalyzed intramolecular site-specific aryl C-H annulation, a highly chemoselective protocol providing direct access to eight-membered sultams/lactams with broad substrate/functional group tolerance. Experimental and computational studies reveal that such a transformation involves a unique PivOH-assisted aryl C-H activation/alkene insertion/β-H elimination/hydrogen-transfer process involving the Rh(III)-hydride species as the active intermediate with the concomitant release of H2 as the major byproduct, thus enabling the developed Cp*CyRh(III) catalysis with redox-neutral and highly atom-economical features.
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