title: 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.
authors.affiliation: Department of Chemistry and Biochemistry, North Dakota State University , Fargo, North Dakota 58102, United States.
authors.forename: Jing
authors.initials: J
authors.lastname: Zhang
authors.forename: Jun-Feng
authors.initials: JF
authors.lastname: Liu
authors.forename: Angel
authors.initials: A
authors.lastname: Ugrinov
authors.forename: Anthony F X
authors.initials: AF
authors.lastname: Pillai
authors.forename: Zhong-Ming
authors.initials: ZM
authors.lastname: Sun
authors.forename: Pinjing
authors.initials: P
authors.lastname: Zhao
mesh_terms: D002384:Catalysis; D062425:Hydroxybenzoate Ethers / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D012238:Rhodium / Q000737:chemistry*
chemical_list: D062425:Hydroxybenzoate Ethers; D009942:Organometallic Compounds; C472445:2,6-dimethoxybenzoic acid; D012238:Rhodium