Catalyst-Controlled Regiodivergence in Rearrangements of Indole-Based Onium Ylides

Vaishnavi N. Nair, Volga Kojasoy, Croix J. Laconsay, Wang Yeuk Kong, Dean J. Tantillo, Uttam K. Tambar

Research output: Contribution to journalArticlepeer-review

10 Scopus citations

Abstract

We have developed catalyst-controlled regiodivergent rearrangements of onium-ylides derived from indole substrates. Oxonium ylides formed in situ from substituted indoles selectively undergo [2,3]- and [1,2]-rearrangements in the presence of a rhodium and a copper catalyst, respectively. The combined experimental and density functional theory (DFT) computational studies indicate divergent mechanistic pathways involving a metal-free ylide in the rhodium catalyzed reaction favoring [2,3]-rearrangement, and a metal-coordinated ion-pair in the copper catalyzed [1,2]-rearrangement that recombines in the solvent-cage. The application of our methodology was demonstrated in the first total synthesis of the indole alkaloid (±)-sorazolon B, which enabled the stereochemical reassignment of the natural product. Further functional group transformations of the rearrangement products to generate valuable synthetic intermediates were also demonstrated.

Original languageEnglish (US)
Pages (from-to)9016-9025
Number of pages10
JournalJournal of the American Chemical Society
Volume143
Issue number24
DOIs
StatePublished - Jun 23 2021

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Fingerprint

Dive into the research topics of 'Catalyst-Controlled Regiodivergence in Rearrangements of Indole-Based Onium Ylides'. Together they form a unique fingerprint.

Cite this