Divergent Synthesis of CF3‐Substituted Allenyl Nitriles by Ligand‐Controlled Radical 1,2‐ and 1,4‐Addition to 1,3‐Enynes

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...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2018-06, Vol.57 (24), p.7140-7145
Main Authors: Wang, Fei, Wang, Dinghai, Zhou, Yu, Liang, Ling, Lu, Ronghua, Chen, Pinhong, Lin, Zhenyang, Liu, Guosheng
Format: Article
Language:English
Subjects:
1,3-enynes
allenyl nitriles
Catalysis
copper
Cyanides
Functional groups
Ligands
Nitriles
Organic chemistry
Organometallic compounds
radical reaction
Radicals
Regioselectivity
Substrates
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Summary: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. 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.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201803668