Computational and Synthetic Investigation of Cationic Rearrangement in the Putative Biosynthesis of Justicane Triterpenoids. (21st December 2018) - Elkin, Masha
Abstract: A biomimetic cationic structural rearrangement of the oleanolic acid framework is reported for the gram‐scale synthesis and structural reassignment of justicioside E aglycone. The mechanism of the putative biosynthetic rearrangement is investigated with kinetic, computational, and synthetic approaches. The precursor to rearrangement was accessed through two strategic advancements: (1) synthesis of a 1, 3‐diketone via oxidation of a β‐silyl enone, and (2) diastereoselective 1, 3‐diketone reduction to form a syn ‐1, 3‐diol using SmI2 with PhSH as a key additive.