Catalytic Ring Expansions of Cyclic Alcohols Enabled by Proton-Coupled Electron Transfer

Kuo Zhao, Kenji Yamashita, Joseph E. Carpenter, Trevor C. Sherwood, William R. Ewing, Peter T.W. Cheng, Robert R. Knowles

Research output: Contribution to journalArticle

18 Scopus citations

Abstract

We report here a catalytic method for the modular ring expansion of cyclic aliphatic alcohols. In this work, proton-coupled electron transfer activation of an allylic alcohol substrate affords an alkoxy radical intermediate that undergoes subsequent C-C bond cleavage to furnish an enone and a tethered alkyl radical. Recombination of this alkyl radical with the revealed olefin acceptor in turn produces a ring-expanded ketone product. The regioselectivity of this C-C bond-forming event can be reliably controlled via substituents on the olefin substrate, providing a means to convert a simple N-membered ring substrate to either n+1 or n+2 ring adducts in a selective fashion.

Original languageEnglish (US)
Pages (from-to)8752-8757
Number of pages6
JournalJournal of the American Chemical Society
Volume141
Issue number22
DOIs
StatePublished - Jun 5 2019

All Science Journal Classification (ASJC) codes

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

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    Zhao, K., Yamashita, K., Carpenter, J. E., Sherwood, T. C., Ewing, W. R., Cheng, P. T. W., & Knowles, R. R. (2019). Catalytic Ring Expansions of Cyclic Alcohols Enabled by Proton-Coupled Electron Transfer. Journal of the American Chemical Society, 141(22), 8752-8757. https://doi.org/10.1021/jacs.9b03973