title: C-O Functionalization of α-Oxyboronates: A Deoxygenative gem-Diborylation and gem-Silylborylation of Aldehydes and Ketones.
abstract: A deoxygenative gem-diborylation and gem-silylborylation of aldehydes and ketones is described. The key for the success of this transformation is the base-promoted C-O bond borylation or silylation of the generated α-oxyboronates. Experimental and theoretical studies exhibit that the C-O bond functionalization proceeds via an intramolecular five-membered transition-state (9-ts) boryl migration followed by a 1,2-metalate rearrangement with OBpin as a leaving group. The transformation occurs with an inversion on the carbon center. Direct conversion of aldehydes and ketones to gem-diboron compounds was achieved by combining copper catalysis with this base-promoted C-OBpin borylation. Various aldehydes and ketones were deoxygenatively gem-diborylated. gem-Silylborylation of aldehydes and ketones were achieved by a stepwise operation, in which B2pin2initially react with those carbonyls followed by a silylation with Bpin-SiMe2Ph.
authors.affiliation: State Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Research Institute of LICP, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences , Lanzhou 730000, P. R. China.
authors.forename: Lu
authors.initials: L
authors.lastname: Wang
authors.affiliation: State Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Research Institute of LICP, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences , Lanzhou 730000, P. R. China.|School of Chemistry and Chemical Engineering, Chongqing University , Chongqing 400030, P. R. China.
authors.forename: Tao
authors.initials: T
authors.lastname: Zhang
authors.affiliation: State Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Research Institute of LICP, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences , Lanzhou 730000, P. R. China.
authors.forename: Wei
authors.initials: W
authors.lastname: Sun
authors.affiliation: State Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Research Institute of LICP, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences , Lanzhou 730000, P. R. China.
authors.forename: Zeyu
authors.initials: Z
authors.lastname: He
authors.affiliation: State Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Research Institute of LICP, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences , Lanzhou 730000, P. R. China.
authors.forename: Chungu
authors.initials: C
authors.lastname: Xia
authors.affiliation: School of Chemistry and Chemical Engineering, Chongqing University , Chongqing 400030, P. R. China.
authors.forename: Yu
authors.initials: Y
authors.lastname: Lan
authors.affiliation: State Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Research Institute of LICP, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences , Lanzhou 730000, P. R. China.
authors.forename: Chao
authors.identifier: http://orcid.org/0000-0002-2521-924X
authors.initials: C
authors.lastname: Liu