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 language | English (US) |
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Pages (from-to) | 5290-5297 |
Number of pages | 8 |
Journal | Journal of the American Chemical Society |
Volume | 98 |
Issue number | 17 |
DOIs | |
State | Published - Aug 1 1976 |
Externally published | Yes |
All Science Journal Classification (ASJC) codes
- Catalysis
- General Chemistry
- Biochemistry
- Colloid and Surface Chemistry