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

preprint
revised on 30.11.2018 and posted on 30.11.2018 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

Exports