Enantioselective Copper-Catalyzed Intermolecular Cyanotrifluoromethylation of Alkenes via Radical Process

A novel enantioselective copper-catalyzed intermolecular cyanotrifluoromethylation of alkenes has been developed, in which a variety of CF -containing alkylnitriles are furnished with excellent enantiomeric excess. Preliminary mechanistic studies revealed (1) the reaction was initiated by a SET proc...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2016-12, Vol.138 (48), p.15547-15550
Main Authors: Wang, Fei, Wang, Dinghai, Wan, Xiaolong, Wu, Lianqian, Chen, Pinhong, Liu, Guosheng
Format: Article
Language:English
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Summary:A novel enantioselective copper-catalyzed intermolecular cyanotrifluoromethylation of alkenes has been developed, in which a variety of CF -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 CF reagent and a Cu(I) catalyst; (2) the released CF 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.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.6b10468