Computational and Synthetic Investigation of Cationic Rearrangement in the Putative Biosynthesis of Justicane Triterpenoids. (21st December 2018)

• Record Type: Journal Article
• Authors: Elkin, Masha; Scruse, Anthony C.; Turlik, Aneta; Newhouse, Timothy R.
• Is Part Of: Angewandte Chemie. Volume 131:Number 4(2019)
• Page Start: 1037
• Page End: 1041
• Publication Date: 2018-12-21
• Subjects: Biomimetische Synthese -- Biosynthese -- Dichtefunktionalrechnungen -- Naturstoffsynthese -- Strukturelle Neuzuordnung; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201810566
• Languages: English
• ISSNs: 0044-8249

Abstract

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.