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Development of a Radical Silylzincation of (Het)Aryl‐Substituted Alkynes and Computational Insights into the Origin of the trans ‐Stereoselectivity
Author(s) -
Romain Elise,
VegaHernández Karen,
Guégan Frédéric,
Sanz García Juan,
Fopp Carolin,
Chemla Fabrice,
Ferreira Franck,
Gerard Hélène,
Jackowski Olivier,
Halbert Stéphanie,
Oestreich Martin,
PerezLuna Alejandro
Publication year - 2021
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.202001566
Subject(s) - stereoselectivity , chemistry , steric effects , aryl , electrophile , stereochemistry , electrophilic addition , computational chemistry , medicinal chemistry , organic chemistry , catalysis , alkyl
Aryl‐ and hetaryl‐substituted acetylenes undergo regio‐ and stereoselective silylzincation by reaction with [(Me 3 Si) 3 Si] 2 Zn in the presence of Et 2 Zn (10–110 mol%) as additive. The distinctive feature of this addition across the C−C triple bond is its trans stereoselectivity. The radical nature of the silylzincation process is supported by diagnostic experiments and DFT calculations, which also corroborate the role played by steric effects to obtain that stereoselectivity. The procedure can be combined in one‐pot with the copper(I)‐mediated electrophilic substitution of the C( sp 2 )−Zn bond, with retention of the double bond geometry. This makes it valuable for the synthesis of stereodefined di‐ and trisubstituted vinylsilanes.