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<p>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.
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Computational and Synthetic Investigation of Cationic Rearrangement in the Putative Biosynthesis of Justicane Triterpenoids
