Synthesis and Analysis of Substituted Bullvalenes

Abstract

Herein we detail a practical synthesis of bullvalene and a variety of mono- and disubstituted analogues through cobalt-catalysed [6+2] cycloaddition of cyclooctatetraene to alkynes, followed by photochemical di-π-methane rearrangement. The application of isomer-network analysis, coupled with quantum-chemical calculations, provides a powerful automated tool for predicting the properties of bullvalene isomer networks.

Keywords: cycloaddition; density functional calculations; photochemistry; sigmatropic rearrangement; valence isomerization.