{"title":"协同光氧化还原/Brønsted酸催化双芳基的对映选择性脱对称及其在菊芋碱全合成中的应用","authors":"Junsoo Moon, Eunjoo Shin and Yongseok Kwon*, ","doi":"10.1021/jacs.5c0148010.1021/jacs.5c01480","DOIUrl":null,"url":null,"abstract":"<p >Photoredox catalysis has emerged as a powerful tool for forming and breaking chemical bonds, further taking hold with its integration with asymmetric catalysis. While the dual-catalytic approach has led to successful examples of the control of stereogenic centers, the control of stereogenic axes has remained underexplored. In this study, an acylimine intermediate was generated through photoredox catalysis, and a symmetric substrate, 2-arylresorcinol, was desymmetrized with the aid of chiral phosphoric acid catalysis. Using this approach, a stereogenic center and stereogenic axis were successfully controlled to provide a natural-product-driven compound. The origins of enantioselectivity and diastereoselectivity were investigated through a density functional theory study of four possible enantiodetermining transition states. Consequently, the first total syntheses of the ring-contracted naphthylisoquinoline alkaloid ancistrobrevolines A and B were accomplished concisely. This approach provides not only a novel methodology and strategy to synthesize naphthylisoquinoline alkaloids but also a direction to advance catalytic research and total synthesis studies.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"147 15","pages":"12800–12810 12800–12810"},"PeriodicalIF":15.6000,"publicationDate":"2025-04-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Enantioselective Desymmetrization of Biaryls via Cooperative Photoredox/Brønsted Acid Catalysis and Its Application to the Total Synthesis of Ancistrobrevolines\",\"authors\":\"Junsoo Moon, Eunjoo Shin and Yongseok Kwon*, \",\"doi\":\"10.1021/jacs.5c0148010.1021/jacs.5c01480\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Photoredox catalysis has emerged as a powerful tool for forming and breaking chemical bonds, further taking hold with its integration with asymmetric catalysis. While the dual-catalytic approach has led to successful examples of the control of stereogenic centers, the control of stereogenic axes has remained underexplored. In this study, an acylimine intermediate was generated through photoredox catalysis, and a symmetric substrate, 2-arylresorcinol, was desymmetrized with the aid of chiral phosphoric acid catalysis. Using this approach, a stereogenic center and stereogenic axis were successfully controlled to provide a natural-product-driven compound. The origins of enantioselectivity and diastereoselectivity were investigated through a density functional theory study of four possible enantiodetermining transition states. Consequently, the first total syntheses of the ring-contracted naphthylisoquinoline alkaloid ancistrobrevolines A and B were accomplished concisely. This approach provides not only a novel methodology and strategy to synthesize naphthylisoquinoline alkaloids but also a direction to advance catalytic research and total synthesis studies.</p>\",\"PeriodicalId\":49,\"journal\":{\"name\":\"Journal of the American Chemical Society\",\"volume\":\"147 15\",\"pages\":\"12800–12810 12800–12810\"},\"PeriodicalIF\":15.6000,\"publicationDate\":\"2025-04-05\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of the American Chemical Society\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/jacs.5c01480\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of the American Chemical Society","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/jacs.5c01480","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
摘要
光氧化催化已成为形成和断开化学键的有力工具,并通过与不对称催化的结合而进一步占据主导地位。虽然双催化方法已经成功地控制了立体中心,但对立体轴的控制仍未得到充分探索。在本研究中,通过光氧化催化生成了酰亚胺中间体,并借助手性磷酸催化对对称底物 2-芳基间苯二酚进行了去对称化。利用这种方法,成功地控制了立体源中心和立体源轴,从而提供了一种天然产物驱动的化合物。通过对四种可能的对映体决定过渡态进行密度泛函理论研究,研究了对映体选择性和非对映体选择性的来源。因此,首次简明地完成了环缩合萘基异喹啉生物碱 ancistrobrevolines A 和 B 的全合成。这种方法不仅为合成萘基异喹啉生物碱提供了一种新的方法和策略,而且为推进催化研究和全合成研究提供了一个方向。
Enantioselective Desymmetrization of Biaryls via Cooperative Photoredox/Brønsted Acid Catalysis and Its Application to the Total Synthesis of Ancistrobrevolines
Photoredox catalysis has emerged as a powerful tool for forming and breaking chemical bonds, further taking hold with its integration with asymmetric catalysis. While the dual-catalytic approach has led to successful examples of the control of stereogenic centers, the control of stereogenic axes has remained underexplored. In this study, an acylimine intermediate was generated through photoredox catalysis, and a symmetric substrate, 2-arylresorcinol, was desymmetrized with the aid of chiral phosphoric acid catalysis. Using this approach, a stereogenic center and stereogenic axis were successfully controlled to provide a natural-product-driven compound. The origins of enantioselectivity and diastereoselectivity were investigated through a density functional theory study of four possible enantiodetermining transition states. Consequently, the first total syntheses of the ring-contracted naphthylisoquinoline alkaloid ancistrobrevolines A and B were accomplished concisely. This approach provides not only a novel methodology and strategy to synthesize naphthylisoquinoline alkaloids but also a direction to advance catalytic research and total synthesis studies.
期刊介绍:
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