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Methoxy-directed aryl-to-aryl 1,3-rhodium migration.

ABSTRACT: 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 sp(3) and sp(2) C-H bond activations.

SUBMITTER: Zhang J 

PROVIDER: S-EPMC4447322 | biostudies-literature | 2013 Nov

REPOSITORIES: biostudies-literature

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Methoxy-directed aryl-to-aryl 1,3-rhodium migration.

Zhang Jing J   Liu Jun-Feng JF   Ugrinov Angel A   Pillai Anthony F X AF   Sun Zhong-Ming ZM   Zhao Pinjing P  

Journal of the American Chemical Society 20131107 46

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-labelin  ...[more]

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