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Updated: Mar 8, 2026

Isolating Free Carbenes, their Mixed Dimers and Organic Radicals
Published on: April 19, 2019
Free-Radical Carbocyanation of Olefins
Haitham Hassan1, Vincent Pirenne1, Maren Wissing1
1Institute of Molecular Sciences, UMR-CNRS 5255, University of Bordeaux, 351, Cours de la libération, 33405, Talence cedex, France.
Abstract:
The free-radical three-component carbocyanation of electron-rich olefins was investigated with p-tosyl cyanide as cyanide source. The scope and limitations of the process were established by varying the nature of the alkene and radical precursor. Carbocyanation of chiral allylsilanes was shown to occur with high diastereocontrol, leading to syn β-silyl nitriles. The origin of the stereocontrol was rationalized by a Felkin-Anh-type transition-state model. Finally, a tin-free carbocyanation process was also devised, based on the use of a new alkylsulfonyl cyanide incorporating both carbon fragments to be added across the olefinic π system.
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