Single-electron/pericyclic cascade for the synthesis of dienes

Natalie E Campbell; Glenn M Sammis

doi:10.1002/anie.201403234

Single-electron/pericyclic cascade for the synthesis of dienes

Angew Chem Int Ed Engl. 2014 Jun 10;53(24):6228-31. doi: 10.1002/anie.201403234. Epub 2014 Apr 29.

Authors

Natalie E Campbell¹, Glenn M Sammis

Affiliation

¹ University of British Columbia, Department of Chemistry, 2036 Main Mall, Vancouver V6T 1Z1 (Canada).

PMID: 24782362
DOI: 10.1002/anie.201403234

Abstract

The highly efficient and diastereoselective synthesis of E dienes has been accomplished through radical cyclization of bromoallyl hydrazones. This methodology has been further extended to generate these products through a one-pot condensation/radical cyclization/cycloreversion cascade from simple aldehyde starting materials in high yields (>75%) and high diastereoselectivities (>95:5). Mechanistic investigations suggest that the cascade reaction proceeds through a cyclic diazene intermediate prior to the cycloreversion.

Keywords: hydrazones; pericyclic reaction; radical reactions; rearrangement; synthetic methods.