New reactions, mechanisms, and stereochemical theory in organic chemistry

Here we describe a new method for the formation of allenes utilizing a Grob-like fragmentation along with a mechanistic study. The mechanism of the azide and thio acid amidation is presented. This mechanism was found to go through a thiatriazoline, and the reaction was successfully extended to the isoelectronic coupling of dithio acids with azides to form thioamide. Finally, distortional asymmetry is presented as new model for understanding stereoselectivity in sterically unbiased systems. This model deomonstrates that small ground state perturbations can lead to significant energy differences between diastereomeric tranistion states.