| Autor: |
Xu W; State Key Laboratory of Chemical Oncogenomics, Lab of Computational Chemistry and Drug Design, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen 518055, China. wuyd@pkusz.edu.cn.; Institute of Chemical Biology, Shenzhen Bay Laboratory, Shenzhen, 518132, China., Sun TY; Institute of Chemical Biology, Shenzhen Bay Laboratory, Shenzhen, 518132, China., Di Y; State Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Institute of Botany, Chinese Academy of Sciences, Kunming 650201, China. haoxj@mail.kib.ac.cn., Hao X; State Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Institute of Botany, Chinese Academy of Sciences, Kunming 650201, China. haoxj@mail.kib.ac.cn., Wu YD; State Key Laboratory of Chemical Oncogenomics, Lab of Computational Chemistry and Drug Design, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen 518055, China. wuyd@pkusz.edu.cn.; Institute of Chemical Biology, Shenzhen Bay Laboratory, Shenzhen, 518132, China.; College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China. |
| Abstrakt: |
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. |
