1. Bioinspired Asymmetric Total Synthesis of Emeriones A–C**
- Author
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Jänner, Sven, Isak, Daniel, Li, Yuli, Houk, Kendall N, and Miller, Aubry K
- Subjects
Cyclization ,Oxidation-Reduction ,Stereoisomerism ,Biomimetic Synthesis ,Cascade Reactions ,Electrocyclizations ,Polyketides ,Total Synthesis ,Chemical Sciences ,Organic Chemistry - Abstract
We report asymmetric bioinspired total syntheses of the fungal metabolites emeriones A-C via stereoselective oxidations of two bicyclo[4.2.0]octadiene diastereomers. The central bicyclic scaffolds are prepared in an 8π/6π electrocyclization cascade of a stereodefined pentaene, which contains the fully assembled side chains of the emeriones. The anti-aldol side chain is made using a Paterson-aldol addition, and the epoxide of the dioxabicyclo[3.1.0]hexane side chain via ring-closure onto an oxidized acetal. Our work has enabled the structural revision of emerione C, and resulted in the synthesis of a "missing" family member, which we call emerione D. DFT calculations identified two methyl groups that govern torquoselectivity in the 8π/6π cascade.
- Published
- 2022