The microwave-assisted oxyanionic 5-exo dig cyclization-Claisen rearrangement process reaction is an expedient route to seven-membered carbocyclic rings often present in natural products. To date, this methodology has been used to generate a variety of racemic cycloheptanoid products; however, it was recently found that this process could be employed for the synthesis of optically enriched materials starting with non-racemic secondary acetylenic alcohol precursors. These were readily prepared from the corresponding ketones via asymmetric reduction using the (–)-CBS reagent. Although the stereogenic center in the starting material is lost in the ensuing tandem reaction, a high level of chirality transfer is observed, suggesting that the thermal Claisen rearrangement proceeds through a chair-like transition state.