Enantioselective Copper-Catalyzed Intermolecular Cyanotrifluoromethylation of Alkenes via Radical Process

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• 作者：Fei Wang ; Dinghai Wang ; Xiaolong Wan ; Lianqian Wu ; Pinhong Chen ; Guosheng Liu
• 刊名：Journal of the American Chemical Society
• 出版年：2016
• 出版时间：December 7, 2016
• 年：2016
• 卷：138
• 期：48
• 页码：15547-15550
• 全文大小：420K
• ISSN：1520-5126

文摘

A novel enantioselective copper-catalyzed intermolecular cyanotrifluoromethylation of alkenes has been developed, in which a variety of CF₃-containing alkylnitriles are furnished with excellent enantiomeric excess. Preliminary mechanistic studies revealed (1) the reaction was initiated by a SET process between activated Togni’s CF₃⁺ reagent and a Cu(I) catalyst; (2) the released CF₃ radical readily added to styrene to provide a benzylic radical, which was then trapped by a chiral Cu(II) cyanide species to deliver the desired alkylnitriles; (3) a low concentration of the CN anion was crucial to obtain high enantioselectivity.