Catalytic Carbocation Generation Enabled by the Mesolytic Cleavage of Alkoxyamine Radical Cations

Qilei Zhu, Emily C. Gentry, Robert R. Knowles

Research output: Contribution to journalArticle

34 Scopus citations

Abstract

A new catalytic method is described to access carbocation intermediates via the mesolytic cleavage of alkoxyamine radical cations. In this process, electron transfer between an excited state oxidant and a TEMPO-derived alkoxyamine substrate gives rise to a radical cation with a remarkably weak C−O bond. Spontaneous scission results in the formation of the stable nitroxyl radical TEMPO.as well as a reactive carbocation intermediate that can be intercepted by a wide range of nucleophiles. Notably, this process occurs under neutral conditions and at comparatively mild potentials, enabling catalytic cation generation in the presence of both acid sensitive and easily oxidized nucleophilic partners.

Original languageEnglish (US)
Pages (from-to)9969-9973
Number of pages5
JournalAngewandte Chemie - International Edition
Volume55
Issue number34
DOIs
StatePublished - 2016

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)

Keywords

  • alkoxyamines
  • carbocations
  • mesolytic cleavage
  • photoredox catalysis
  • radical cations

Fingerprint Dive into the research topics of 'Catalytic Carbocation Generation Enabled by the Mesolytic Cleavage of Alkoxyamine Radical Cations'. Together they form a unique fingerprint.

  • Cite this