Divergent Synthesis of CF3‐Substituted Allenyl Nitriles by Ligand‐Controlled Radical 1,2‐ and 1,4‐Addition to 1,3‐Enynes |
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| Authors: | Fei Wang Dinghai Wang Yu Zhou Ling Liang Ronghua Lu Dr Pinhong Chen Prof?Dr Zhenyang Lin Prof?Dr Guosheng Liu |
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| Affiliation: | 1. http://guoshengliu.sioc.ac.cn/;2. State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai, China;3. Department of Chemistry, The Hong Kong University of Science and Technology, Kowloon, Hong Kong, China |
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| Abstract: | A ligand‐controlled system that enables regioselective trifluoromethylcyanation of 1,3‐enynes has been identified, which provides access to a variety of CF3‐containing tri‐ and tetrasubstituted allenyl nitriles. We disclose that the involved propargylic radicals can be selectively trapped by (Box)CuII cyanide, while the tautomerized allenyl radicals are trapped by (phen)CuII cyanide (Box= bisoxazoline, phen=phenanthroline). In addition, the reaction features broad substrate scope and excellent functional group compatibility. Moreover, this protocol represents a novel regioselectivity‐tunable functionalization of 1,3‐enynes via radicals, which we believe will have great implications for the development of catalytic systems for selectivity control in radical and organometallic chemistry. |
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| Keywords: | 1 3-enynes allenyl nitriles copper radical reaction regioselectivity |
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