En route to the total synthesis of tashironin: on the exercise of stereochemical control by a methyl group in mediating remote cyclization reactions

The synthesis of the [2.2.2]-bicyclic core (23) of the neurotrophic factor 11-O-debenzoyltashironin (1) has been achieved by an oxidative dearomatization-transannular Diels-Alder cascade. We have shown that the reaction sequence is also valuable for the efficient construction of related, complex [2.2.2]-bicyclic compounds (vide infra).