Au-catalyzed skeletal rearrangement of O-propargylic oximes via N-O bond cleavage with the aid of a Brønsted base cocatalyst

Research output: Contribution to journalArticle

Abstract

O-Propargylic oximes that possess an electron-withdrawing aryl group on the oxime moiety undergo Au-catalyzed skeletal rearrangements via N-O bond cleavage to afford the corresponding 2H-1,3-oxazine derivatives. Our studies show that the inclusion of a Brønsted base cocatalyst not only accelerates the reaction but also switches pathways of the skeletal rearrangement reaction, realizing divergent synthesis of heterocyclic compounds. Computational studies indicate that the elimination of propargylic proton in the cyclized vinylgold intermediate is rate-determining and both electron-withdrawing substituents at the oxime moiety and base cocatalyst facilitate the proton elimination. Moreover, the protodeauration process proceeds stepwise involving N-O bond cleavage followed by recyclization to construct the oxazine core.

Original languageEnglish
Pages (from-to)5283-5289
Number of pages7
JournalChemical Science
Volume10
Issue number20
DOIs
Publication statusPublished - 2019 Jan 1

ASJC Scopus subject areas

  • Chemistry(all)

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