Synthesis 2017; 49(04): 724-735
DOI: 10.1055/s-0036-1588106
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© Georg Thieme Verlag Stuttgart · New York

Stereodivergent Synthesis of β-Heteroatom-Substituted Vinyl­silanes by Sequential Silylzincation–Copper(I)-Mediated Electrophilic­ Substitution

Carolin Foppa, Kevin Isaacb, Elise Romainb, Fabrice Chemlab, Franck Ferreirab, Olivier Jackowskib, Martin Oestreich*a, Alejandro Perez-Luna*b
  • aInstitut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 115, 10623 Berlin, Germany   Email: martin.oestreich@tu-berlin.de
  • bSorbonne Universités, UPMC Univ Paris 06, CNRS UMR 8232, Institut Parisien de Chimie Moléculaire (IPCM), Case 229, 4 place Jussieu, 75005 Paris, France   Email: alejandro.perez_luna@upmc.fr
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Publication History

Received: 31 October 2016

Accepted after revision: 04 November 2016

Publication Date:
17 November 2016 (eFirst)

Abstract

Sulfur-, oxygen-, and phosphorus-substituted terminal alkynes undergo regio- and stereoselective silylzincation by reaction with (Me2PhSi)2Zn, (Me3Si)3SiH/Et2Zn or [(Me3Si)3Si]2Zn/Et2Zn. The addition across the C–C triple bond always occurs with β-regioselectivity but the stereoselectivity is tunable: (Me2PhSi)2Zn for cis and (Me3Si)3SiH/­Et2Zn or [(Me3Si)3Si]2Zn/Et2Zn for trans. The procedures making use of the zinc reagents (Me2PhSi)2Zn and [(Me3Si)3Si]2Zn can be combined in one-pot with a subsequent stereoretentive copper(I)-mediated electrophilic substitution of the intermediate C(sp2)–Zn bond. These stereodivergent protocols offer a regio- and stereoselective access to trisubstituted vinylsilanes decorated with sulfur-, oxygen-, and phosphorus substituents with either double-bond geometry.

Supporting Information