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13 C NMR studies: XLVI—rearrangements and deuterium exchange via homoenolization in bicyclooctanones. A convenient preparation of bicyclic β,γ‐ and γ,δ‐unsaturated ketones
Author(s) -
Hudyma D. M.,
Stothers J. B.,
Tan C. T.
Publication year - 1974
Publication title -
organic magnetic resonance
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.483
H-Index - 72
eISSN - 1097-458X
pISSN - 0030-4921
DOI - 10.1002/mrc.1270061114
Subject(s) - deuterium , bicyclic molecule , conjugated system , chemistry , medicinal chemistry , stereochemistry , organic chemistry , physics , nuclear physics , polymer
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.