American Chemical Society
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Rearrangement of 5-Trimethylsilylthebaine on Treatment with L-Selectride:  An Efficient Synthesis of (+)-Bractazonine

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journal contribution
posted on 2003-02-08, 00:00 authored by Weibin 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.