Stereospecific Aliphatic Hydroxylation by Iron-Hydrogen Peroxide. Evidence for a Stepwise Process

John Taylor Groves, Michael Van Der Puy

Research output: Contribution to journalArticle

140 Scopus citations

Abstract

Treatment of a mixture of cyclohexanol and ferrous perchlorate with hydrogen peroxide in acetonitrile led to a mixture of cyclohexanediols and cyclohexanone. In acetohitrile containing perchloric acid, cis-1,3-cyclohexanediol accounted for 71.9% of the diol produced. Under these conditions, hydrogen removal at C-3 occurred stereoselectively cis to the hydroxyl group. A mechanism for this aliphatic hydroxylation which involves an initial directed hydrogen abstraction (kH/kD = 1.18), free radical oxidation by Fe3+, and stereoselective carbonium ion capture was proposed. Evidence for the stepwise nature of this process was derived from analysis of the Fe2+/H2O2 oxidation of 7-hydroxynorbornane (6). Hydrogen abstraction from 6 was found to occur stereoselectively syn to the hydroxyl group and subsequent 2,6-hydride transfers result in a 1:1 ratio of syn.exo and anti,exo diols (8 and 9).

Original languageEnglish (US)
Pages (from-to)5290-5297
Number of pages8
JournalJournal of the American Chemical Society
Volume98
Issue number17
DOIs
StatePublished - Aug 1 1976
Externally publishedYes

All Science Journal Classification (ASJC) codes

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

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