Direct Access to Trifluoromethylated Benzo[d]oxepines from o-Alkynylaryl Aldehydes and Trifluorodiazoethane.

Abstract

Reported in this Letter is a silver-catalyzed reaction between o-alkynylaryl aldehydes and trifluorodiazoethane that enables an expedient synthesis of trifluoromethylated benzo[d]oxepines. The reaction works through a silver-promoted 6-endo-dig cyclization of o-alkynylbenzaldehydes for the generation of an isochromenylium intermediate, which upon a ring-expansive addition of trifluorodiazoethane delivers a novel class of trifluoromethylated benzoxepine frameworks. This strategy was applied to the synthesis of phosphonylated benzo[d]oxepines using the Seyferth-Gilbert reagent.