The Ovaska lab has demonstrated synthesis of cycloheptanoid and cyclooctanoid compounds by base-catalyzed μ–wave assisted tandem and 5- and 6-exo dig cyclization/Claisen rearrangement with the installation of sufficient electron withdrawing groups at the triple bond terminus.1 The Ovaska lab has also shown facile cyclooctanoid synthesis in μ–wave assisted tandem 6-exo dig cyclization/Claisen rearrangement.2 More recently, by the utilization of the Thorpe-Ingold effect, installation of gem-dimethyl moieties α to the hydroxyl position of 5-hexyn-1-ols demonstrated enhanced tandem cyclization and rearrangement.3 This thesis extrapolates the Thorpe-Ingold effect and demonstrates that facile cyclization is maintained when the geminal-dimethyl moiety is placed β to the hydroxyl position of 5-hexyn-1-ols as well. This research expands upon the β gem-dimethyl moiety’s promotion of cyclization by demonstrating substituted cyclization of derivatives of the 3,3- dimethylhex-5-yn-1-ol precursor. Additionally, the scope of the prototypical Thorpe-Ingold enhancement is expanded to an ongoing study of a gem-dimethyl substitution γ to the hydroxyl in the pursuit of soundly demonstrating the methodology’s robust application to cyclooctanoid synthesis.
DeLomba, Weston, "The Thorpe-Ingold Effect Promotes Tandem 6-exo Dig Cyclization/Claisen Rearrangement" (2018). Chemistry Honors Papers. 24.
The views expressed in this paper are solely those of the author.