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

preprint
revised on 30.11.2018, 16:02 and posted on 30.11.2018, 16:02 by Masha Elkin, Anthony Scruse, Aneta Turlik, Timothy Newhouse

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.

History

Email Address of Submitting Author

timothy.newhouse@yale.edu

Institution

Yale University

Country

United States

ORCID For Submitting Author

0000-0001-8741-7236

Declaration of Conflict of Interest

No conflict of interest

Version Notes

Version 1.0

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