Divergent Synthesis of CF3‐Substituted Allenyl Nitriles by Ligand‐Controlled Radical 1, 2‐ and 1, 4‐Addition to 1, 3‐Enynes. Issue 24 (14th May 2018)

• Record Type: Journal Article
• Authors: Wang, Fei; Wang, Dinghai; Zhou, Yu; Liang, Ling; Lu, Ronghua; Chen, Pinhong; Lin, Zhenyang; Liu, Guosheng
• Is Part Of: Angewandte Chemie international edition. Volume 57:Issue 24(2018)
• Page Start: 7140
• Page End: 7145
• Publication Date: 2018-05-14
• Subjects: 1, 3-enynes -- allenyl nitriles -- copper -- radical reaction -- regioselectivity; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201803668
• Languages: English
• ISSNs: 1433-7851

Abstract

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)Cu II cyanide, while the tautomerized allenyl radicals are trapped by (phen)Cu II 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. Abstract : Two flavors : A ligand‐controlled radical 1, 2‐ and 1, 4‐addition to 1, 3‐enynes provides access to a variety of CF3 ‐containing tri‐ and tetrasubstituted allenyl nitriles. The reaction features broad substrate scope and excellent functional group compatibility. This protocol represents a novel regioselectivity‐tunable functionalization of 1, 3‐enynes via radicals.