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Divergent Synthesis of CF 3 ‐Substituted Allenyl Nitriles by Ligand‐Controlled Radical 1,2‐ and 1,4‐Addition to 1,3‐Enynes
Author(s) -
Wang Fei,
Wang Dinghai,
Zhou Yu,
Liang Ling,
Lu Ronghua,
Chen Pinhong,
Lin Zhenyang,
Liu Guosheng
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201803668
Subject(s) - regioselectivity , radical , chemistry , cyanide , combinatorial chemistry , catalysis , ligand (biochemistry) , substrate (aquarium) , phenanthroline , organic chemistry , biochemistry , receptor , oceanography , geology
Abstract A ligand‐controlled system that enables regioselective trifluoromethylcyanation of 1,3‐enynes has been identified, which provides access to a variety of CF 3 ‐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.