Formation of o-Allyl- and Allenyl-Modified Amides via Intermolecular Claisen Rearrangement

Org Lett. 2021 Feb 19;23(4):1315-1320. doi: 10.1021/acs.orglett.0c04300. Epub 2021 Feb 3.

Abstract

We developed a new transition-metal-free intermolecular Claisen rearrangement process to introduce allyl and allenyl groups into the α position of tertiary amides. In this transformation, amides were activated by trifluoromethanesulfonic anhydride to produce the keteniminium ion intermediates that exhibit strong electrophilic activity. This atom-economical process delivers α position-modified amides under mild conditions in moderate to good yields and showcases a broad substrate compatibility.