Substituent-Controlled Copper-Catalyzed Trifluoromethylation of 1,7-Dienes: Synthesis of Mono- and Bis-trifluoromethylated Benzoxepines

A copper-catalyzed trifluoromethylation of benzene-linked 1,7-dienes with 1-trifluoromethyl-1,2-benziodoxole via a radical cascade cyclization process for the synthesis of mono- and bis-trifluoromethylated benzoxepines is developed. The selectivity depends on substituents on the double bond of the allyl group in 1,7-dienes. The large-scale operation and late-stage functionalization of bioactive molecules reveal the promising utility of this protocol.