title: Iridium-Catalyzed, Hydrosilyl-Directed Borylation of Unactivated Alkyl C-H Bonds.
abstract: We report the iridium-catalyzed borylation of primary and secondary alkyl C-H bonds directed by a Si-H group to form alkylboronate esters site selectively. The reactions occur with high selectivity at primary C-H bonds γ to the hydrosilyl group to form primary alkyl bisboronate esters. In the absence of such primary C-H bonds, the borylation occurs selectively at a secondary C-H bond γ to the hydrosilyl group, and these reactions of secondary C-H bonds occur with high diastereoselectivity. The hydrosilyl-containing alkyl boronate esters formed by this method undergo transformations selectively at the carbon-boron or carbon-silicon bonds of these products under distinct conditions to give the products of amination, oxidation, and arylation.
authors.affiliation: Department of Chemistry, University of California , Berkeley, California 94720, United States.
authors.forename: Matthew A
authors.initials: MA
authors.lastname: Larsen
authors.affiliation: Department of Chemistry, University of California , Berkeley, California 94720, United States.
authors.forename: Seung Hwan
authors.initials: SH
authors.lastname: Cho
authors.affiliation: Department of Chemistry, University of California , Berkeley, California 94720, United States.
authors.forename: John
authors.initials: J
authors.lastname: Hartwig
mesh_terms: D001897:Boronic Acids / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D004952:Esters / Q000138:chemical synthesis* / Q000737:chemistry; D007495:Iridium / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D012821:Silanes / Q000737:chemistry*
chemical_list: D001897:Boronic Acids; D004952:Esters; D009942:Organometallic Compounds; D012821:Silanes; D007495:Iridium