title: Stereodivergent Silylzincation of α-Heteroatom-Substituted Alkynes.
abstract: Zinc reagents (Me2PhSi)2Zn and [(Me3Si)3Si]2Zn undergo highly regio- and stereoselective addition across the carbon-carbon triple bond of nitrogen-, sulfur-, oxygen-, and phosphorus-substituted terminal alkynes in the absence of copper or any other catalyst. Both reagents yield exclusively β-isomers, and the stereoselectivity is determined by the silyl group: Me2PhSi for cis or (Me3Si)3Si for trans. These stereodivergent silylzincation protocols offer an efficient access to heteroatom-substituted vinylsilanes with either double bond geometry, including trisubstituted vinylsilanes by one-pot electrophilic substitution of the intermediate C(sp(2))-Zn bond by copper(I)-mediated carbon-carbon bond formation.
authors.affiliation: Institut für Chemie, Technische Universität Berlin , Strasse des 17. Juni 115, D-10623 Berlin, Germany.
authors.forename: Carolin
authors.initials: C
authors.lastname: Fopp
authors.affiliation: Sorbonne Universités, UPMC Univ Paris 06 , CNRS UMR 8232, Institut Parisien de Chimie Moléculaire (IPCM), 4, place Jussieu, F-75005 Paris, France.
authors.forename: Elise
authors.initials: E
authors.lastname: Romain
authors.affiliation: Sorbonne Universités, UPMC Univ Paris 06 , CNRS UMR 8232, Institut Parisien de Chimie Moléculaire (IPCM), 4, place Jussieu, F-75005 Paris, France.
authors.forename: Kevin
authors.initials: K
authors.lastname: Isaac
authors.affiliation: Sorbonne Universités, UPMC Univ Paris 06 , CNRS UMR 8232, Institut Parisien de Chimie Moléculaire (IPCM), 4, place Jussieu, F-75005 Paris, France.
authors.forename: Fabrice
authors.initials: F
authors.lastname: Chemla
authors.affiliation: Sorbonne Universités, UPMC Univ Paris 06 , CNRS UMR 8232, Institut Parisien de Chimie Moléculaire (IPCM), 4, place Jussieu, F-75005 Paris, France.
authors.forename: Franck
authors.initials: F
authors.lastname: Ferreira
authors.affiliation: Sorbonne Universités, UPMC Univ Paris 06 , CNRS UMR 8232, Institut Parisien de Chimie Moléculaire (IPCM), 4, place Jussieu, F-75005 Paris, France.
authors.forename: Olivier
authors.initials: O
authors.lastname: Jackowski
authors.affiliation: Institut für Chemie, Technische Universität Berlin , Strasse des 17. Juni 115, D-10623 Berlin, Germany.
authors.forename: Martin
authors.initials: M
authors.lastname: Oestreich
authors.affiliation: Sorbonne Universités, UPMC Univ Paris 06 , CNRS UMR 8232, Institut Parisien de Chimie Moléculaire (IPCM), 4, place Jussieu, F-75005 Paris, France.
authors.forename: Alejandro
authors.initials: A
authors.lastname: Perez-Luna