Chemo- and Diastereoselective Acylfluorination of Nonactivated Olefins to Access Benzo[b]azepines.

Abstract

Here, we describe a transition-metal-free condition that realized the intramolecular acylfluorination of unactivated olefins. It was designed to access seven-membered-ring-containing benzo[b]annulenones from readily prepared 2-allylamino benzoic acids. The formation of a broad scope of electronically and sterically varied benzo[b]annulenones was demonstrated (>30 examples, up to 88% yield and >20:1 dr ratio). Mechanistic studies indicated that the in situ formed XatlFluor-E-activated anhydride was the active species and induced an electrophilic 7-endo-trig cyclization, followed by fluoride capture of the cation.