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Wagner-Meerwein rearrangement of a [3.3.3]- to a [4.3.3]propellane: deuterium tracer and conformational analysis

✍ Scribed by Benito Reyes-Trejo; Martha S. Morales-Ríos; Pedro Joseph-Nathan

Publisher
John Wiley and Sons
Year
2007
Tongue
English
Weight
400 KB
Volume
45
Category
Article
ISSN
0749-1581

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✦ Synopsis

Abstract

Formation of (−)‐[4.3.3]propellane 4 from (−)‐14‐hydroxymodhephene (2) proceeds through a Wagner‐Meerwein rearrangement via C3C4 bond‐shift to give a stable intermediate, dimethylcyclohexadienyl cation A, which undergoes deprotonation. Herein, this mechanism was investigated by using a deuterium labeled substrate at the C‐14 methylene group of (−)‐2, which was incorporated into the C‐4 position of (−)‐[4.3.3]propellane 4. The stereostructure of (−)‐4 was investigated by applying a combination of NMR experimental and theoretical approaches. Copyright © 2007 John Wiley & Sons, Ltd.

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