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

Divergent Synthesis of CF3-Substituted Allenyl Nitriles by Ligand-Controlled Radical 1,2- and 1,4-Addition of 1,3-Enynes.
Angew Chem Int Ed Engl. 2018 Apr 17;:
Authors: Liu G, Wang F, Wang D, Liang L, Lu R, Chen P, Lin Z, Zhou Y
Abstract
A ligand-controlled system that enables regioselective trifluoromethylcyanation of 1,3-enynes has been identified, which provides an access to a variety of CF3-containing tri- and tetra-substituted 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. 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 potential implications for the development of catalytic systems for selectivity control in radical and organometallic chemistry.
PMID: 29667331 [PubMed - as supplied by publisher]

Source: Angewandte Chemie - April 17, 2018 Category: Chemistry Authors: Liu G, Wang F, Wang D, Liang L, Lu R, Chen P, Lin Z, Zhou Y Tags: Angew Chem Int Ed Engl Source Type: research