Free-Radical Carbocyanation of Olefins.

Authors :: Hassan H
Pirenne V
Wissing M
Khiar C
Hussain A
Robert F
Landais Y
Source :: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2017 Apr 03; Vol. 23 (19), pp. 4651-4658. Date of Electronic Publication: 2017 Mar 15.
Publication Year :: 2017
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.<br /> (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)