{"title":"全面了解生物仿生全合成布雷维纳酰胺 A 的机理。","authors":"Wenqiang Xu, Tian-Yu Sun, Yingtong Di, Xiaojiang Hao, Yun-Dong Wu","doi":"10.1039/d4ob00915k","DOIUrl":null,"url":null,"abstract":"<p><p>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.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9000,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"A comprehensive understanding of the mechanism of the biomimetic total synthesis of brevianamide A.\",\"authors\":\"Wenqiang Xu, Tian-Yu Sun, Yingtong Di, Xiaojiang Hao, Yun-Dong Wu\",\"doi\":\"10.1039/d4ob00915k\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>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.</p>\",\"PeriodicalId\":96,\"journal\":{\"name\":\"Organic & Biomolecular Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.9000,\"publicationDate\":\"2024-09-18\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organic & Biomolecular Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1039/d4ob00915k\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, ORGANIC\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organic & Biomolecular Chemistry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d4ob00915k","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
引用次数: 0
摘要
最近,有关化学合成布雷维那酰胺 A(BA)的几项研究得到了报道。其中,Lawrence 的研究小组报道了一种高效且具有显著选择性的合成策略。然而,人们对这些结果仍缺乏统一的机理认识。我们开展了一项 DFT 研究,并提出了一种统一的机理来理解这些实验结果。从中间体 2 开始,最有利的反应顺序是快速同分异构,然后是碱基分子的 σ 迁移,最后是反电子需求的 Diels-Alder 反应,从而立体选择性地形成 BA 产物。这一反应机理也可用于理解涉及酶催化的 BA 生物合成。
A comprehensive understanding of the mechanism of the biomimetic total synthesis of brevianamide A.
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.