1,3-Alkyl Transposition in Allylic Alcohols Enabled by Proton-Coupled Electron Transfer

Kuo Zhao, Gesa Seidler, Robert R. Knowles

Research output: Contribution to journalArticlepeer-review

Abstract

A method is described for the isomerization of acyclic allylic alcohols into β-functionalized ketones via 1,3-alkyl transposition. This reaction proceeds via light-driven proton-coupled electron transfer (PCET) activation of the O−H bond in the allylic alcohol substrate, followed by C−C β-scission of the resulting alkoxy radical. The transient alkyl radical and enone acceptor generated in the scission event subsequently recombine via radical conjugate addition to deliver β-functionalized ketone products. A variety of allylic alcohol substrates bearing alkyl and acyl migratory groups were successfully accommodated. Insights from mechanistic studies led to a modified reaction protocol that improves reaction performance for challenging substrates.

Original languageEnglish (US)
Pages (from-to)20190-20195
Number of pages6
JournalAngewandte Chemie - International Edition
Volume60
Issue number37
DOIs
StatePublished - Sep 6 2021

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)

Keywords

  • alkoxy radicals
  • C−C cleavage
  • isomerization
  • PCET
  • photocatalysis

Fingerprint

Dive into the research topics of '1,3-Alkyl Transposition in Allylic Alcohols Enabled by Proton-Coupled Electron Transfer'. Together they form a unique fingerprint.

Cite this