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Methoxy-Directed Aryl-to-Aryl 1,3-Rhodium Migration

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posted on 20.11.2013, 00:00 by Jing Zhang, Jun-Feng Liu, Angel Ugrinov, Anthony F. X. Pillai, Zhong-Ming Sun, Pinjing Zhao
Through-space metal/hydrogen shift is an important strategy for transition-metal-catalyzed C–H bond activation. Here we describe the synthesis and characterization of a Rh­(I) 2,6-dimethoxybenzoate complex that underwent stoichiometric rearrangement via a highly unusual 1,3-rhodium migration. This aryl-to-aryl 1,3-Rh/H shift was also demonstrated in a Rh­(I)-catalyzed decarboxylative conjugate addition to form a C–C bond at a meta position instead of the ipso-carboxyl position. A deuterium-labeling study under the conditions of Rh­(I)-catalyzed protodecarboxylation revealed the involvement of an ortho-methoxy group in a multistep pathway of consecutive sp3 and sp2 C–H bond activations.