✦ LIBER ✦
13C NMR studies: XLVI—rearrangements and deuterium exchange via homoenolization in bicyclooctanones. A convenient preparation of bicyclic β,γ- and γ,δ-unsaturated ketones
✍ Scribed by D. M. Hudyma; J. B. Stothers; C. T. Tan
- Publisher
- John Wiley and Sons
- Year
- 1974
- Tongue
- English
- Weight
- 228 KB
- Volume
- 6
- Category
- Article
- ISSN
- 0749-1581
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✦ Synopsis
Abstract
With t‐BuO^−^/t‐BuOH at 185°C bicyclo‐[2.2.2] and ‐[3.2.1]octanones are interconvertible. In saturated systems equilibrium is attained very slowly, but in unsaturated cases an equilibrium mixture heavily favoring the [3.2.1] skeleton is obtained relatively rapidly, thereby providing a convenient route to homo and bis‐homo conjugated ketones. Experiments in t‐BuOD using ^13^C NMR to monitor deuterium incorporation revealed five major sites of exchange in the unsaturated ketones.