Directed, Remote Dirhodium C(sp3)-H Functionalization, Desaturative Annulation, and Desaturation

Sailu Munnuri, John R. Falck

Research output: Contribution to journalArticlepeer-review

1 Scopus citations

Abstract

Iminodirhodium reactive intermediates generated in situ from O-tosyloximes using Rh2(esp)2 in CH2Cl2 at rt were exploited for an agile trichotomy of challenging transformations: (1) remote C-H functionalizations using an exceptionally broad diversity of inorganic and organic nucleophiles including several unconventional examples, for example, ethers and acyl silanes; (2) desaturative annulation, a biomimetic 1,3-methylene C-C ring-closure with an overall loss of two hydrogens; and (3) directed desaturation for the acceptor-less, regioselective creation of γ,δ- or γ,δ,ϵ,ζ-olefins. Compared with typical iminyl transition-metal-mediated and 1,5-hydrogen atom-transfer (1,5-HAT) processes, iminodirhodium intermediates are largely underexplored, especially with respect to C(sp3)-H centers and, yet, have the potential to be transformative by virtue of their substrate breadth, regiocontrol, and elusive reaction modality. A substrate scope includes benzylic, allylic, propargylic, tertiary, and α-alkyloxy centers.

Original languageEnglish (US)
Pages (from-to)17989-17998
Number of pages10
JournalJournal of the American Chemical Society
Volume144
Issue number39
DOIs
StatePublished - Oct 5 2022

ASJC Scopus subject areas

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

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