Computational and Synthetic Investigation of Cationic Rearrangement in the Putative Biosynthesis of Justicane Triterpenoids

30 November 2018, Version 2
This content is a preprint and has not undergone peer review at the time of posting.

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.

Keywords

natural product synthesis
computational chemistry
terpenes

Supplementary materials

Title
Description
Actions
Title
Justicane-Newhouse
Description
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Title
Justicane-Newhouse-SI
Description
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