posted on 2003-02-08, 00:00authored byWeibin Chen, Huifang Wu, Denzil Bernard, Matthew D. Metcalf, Jeffrey R. Deschamps, Judith L. Flippen-Anderson, Alexander D. MacKerell,, Andrew Coop
Treatment of 5-trimethylsilylthebaine with L-Selectride gave rise to a rearrangement to 10-trimethylsilylbractazonine through migration of the phenyl group, whereas treatment of thebaine
with strong Lewis acids is known to lead to a similar rearrangement through migration of the
alkyl bridge to give, after reduction, (+)-neodihydrothebaine. It is suggested that the rearrangement
of the alkyl group of thebaine is favored due to the formation of a tertiary benzylic cation. However,
for 5-trimethylsilylthebaine, the lithium ion of L-Selectride acts as the Lewis acid and the β-silyl
effect dominates in the stabilization of any positive charge. This rearrangement provides a clear
example of the greater relative migratory aptitude of phenyl groups over alkyl groups, and provides
an efficient synthesis of (+)-bractazonine from thebaine.