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

Benito Reyes-Trejo; Martha S Morales-Ríos; Pedro Joseph-Nathan

doi:10.1002/mrc.1978

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

Magn Reson Chem. 2007 Apr;45(4):346-50. doi: 10.1002/mrc.1978.

Authors

Benito Reyes-Trejo¹, Martha S Morales-Ríos, Pedro Joseph-Nathan

Affiliation

¹ Laboratorio de Productos Naturales, Area de Química, Universidad Autónoma Chapingo, Apartado 74, Oficina de Correos Chapingo, Texcoco, México, 56230, México.

PMID: 17351977
DOI: 10.1002/mrc.1978

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.