Hassan Haitham, Pirenne Vincent, Wissing Maren, Khiar Chahinaz, Hussain Ashique, Robert Frédéric, Landais Yannick
Institute of Molecular Sciences, UMR-CNRS 5255, University of Bordeaux, 351, Cours de la libération, 33405, Talence cedex, France.
Laboratoire de Chimie Appliquée et du Génie Chimique (LCAGC), Université Mouloud Mammerie de Tizi-Ouzou, 15000, Tizi-Ouzou, Algeria.
Chemistry. 2017 Apr 3;23(19):4651-4658. doi: 10.1002/chem.201605946. Epub 2017 Mar 15.
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.
以对甲苯磺酰氰为氰源，研究了富电子烯烃的自由基三组分碳氰化反应。通过改变烯烃和自由基前体的性质，确定了该反应的适用范围和局限性。结果表明，手性烯丙基硅烷的碳氰化反应具有高非对映选择性，生成顺式β-硅基腈。通过费尔金-安（Felkin-Anh）型过渡态模型对立体控制的起源进行了合理化解释。最后，基于使用一种新的烷基磺酰氰设计了一种无锡碳氰化反应过程，该烷基磺酰氰包含要跨烯烃π体系添加的两个碳片段。
