1. A comprehensive understanding of the mechanism of the biomimetic total synthesis of brevianamide A.
- Author
-
Xu W, Sun TY, Di Y, Hao X, and Wu YD
- Subjects
- Stereoisomerism, Molecular Structure, Biomimetics, Biomimetic Materials chemistry, Biomimetic Materials chemical synthesis, Cycloaddition Reaction, Density Functional Theory
- Abstract
Recently, several studies on the chemical synthesis of brevianamide A (BA) were reported. In particular, a highly efficient and remarkably selective synthetic strategy was reported by Lawrence's group. However, a unified mechanistic understanding of these results is still lacking. We have carried out a DFT study and proposed a unified mechanism to understand these experimental results. Starting from intermediate 2, the most favorable reaction sequence is a fast tautomerization, followed by a σ-migration of the base moiety, and a final inverse-electron demanding Diels-Alder reaction, resulting in the formation of the BA product stereoselectively. This reaction mechanism can also be applied to understand the biosynthesis of BA that involves enzymatic catalysis.
- Published
- 2024
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