Kornblum unsymmetrical olefin synthesis employing radical-anion chain crossed-coupling (light catalysed) of a mono-and a gem-di-nitro-compound, followed by reductive NO2 removal, is examined in the context of a hindered olefin structure required for phytuberin synthesis. Whilst successful for a tetrasubstituted olefin model (for which a Wittig approach failed), increasing substitution on the β-position of the mononitro component supressed ...