title: Stereocontrolled Synthesis of Vinyl Boronates and Vinyl Silanes via Atom-Economical Ruthenium-Catalyzed Alkene-Alkyne Coupling.
abstract: The synthesis of vinyl boronates and vinyl silanes was achieved by employing a Ru-catalyzed alkene-alkyne coupling reaction of allyl boronates or allyl silanes with various alkynes. The double bond geometry in the generated vinyl boronates can be remotely controlled by the juxtaposing boron- and silicon groups on the alkyne substrate. The synthetic utility of the coupling products has been demonstrated in a variety of synthetic transformations, including iterative cross-coupling reactions, and a Chan-Lam-type allyloxylation followed by a Claisen rearrangement. A sequential one-pot alkene-alkyne-coupling/allylation-sequence with an aldehyde to deliver a highly complex α-silyl-β-hydroxy olefin with a handle for further functionalization was also realized.
authors.affiliation: Department of Chemistry, Stanford University, Stanford, CA 94305-5080 (USA). bmtrost@stanford.edu.
authors.forename: Barry M
authors.initials: BM
authors.lastname: Trost
authors.affiliation: Department of Chemistry, Stanford University, Stanford, CA 94305-5080 (USA).
authors.forename: Dennis C
authors.initials: DC
authors.lastname: Koester
authors.affiliation: Department of Chemistry, Stanford University, Stanford, CA 94305-5080 (USA).
authors.forename: Alastair N
authors.initials: AN
authors.lastname: Herron
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D000480:Alkynes / Q000737:chemistry*; D001897:Boronic Acids / Q000138:chemical synthesis*; D002384:Catalysis; D012428:Ruthenium / Q000737:chemistry*; D014753:Vinyl Compounds / Q000138:chemical synthesis*
chemical_list: D000475:Alkenes; D000480:Alkynes; D001897:Boronic Acids; D014753:Vinyl Compounds; D012428:Ruthenium
keywords: atom economy; boron; cross-coupling; homogeneous catalysis; ruthenium