{"title":"硅烯醇醚的催化不对称异构化/硼化反应","authors":"Yisen Yao, Jintao Sun, Jie Li, Wanxiang Zhao","doi":"10.1039/d5sc04819b","DOIUrl":null,"url":null,"abstract":"Asymmetric remote hydroboration of olefins has emerged as an efficient strategy for the construction of chiral boronic esters. Conventional asymmetric alkene isomerizations rely on directing groups (OH, NR<small><sub>2</sub></small>, carbonyl) for thermodynamic control <em>via</em> (hyper)conjugation, but their use restricts substrate scope and risks β-heteroatom elimination with transition-metal catalysts. We here reported a catalytic asymmetric isomerization/hydroboration of silyl enol ethers under mild conditions, enabling the efficient synthesis of enantioenriched boryl ethers. The chiral borylether products enable efficient access to valuable 1,<em>n</em>-diols and 1,<em>n</em>-amino alcohols, prevalent in bioactive molecules, and facilitate late-stage functionalization of complex architectures. Preliminary mechanistic studies reveal that this reaction involves a nondissociative chain-walking process and that the β-H elimination may contribute to the rate-limiting step.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"8 1","pages":""},"PeriodicalIF":7.4000,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Catalytic asymmetric isomerization/hydroboration of silyl enol ethers\",\"authors\":\"Yisen Yao, Jintao Sun, Jie Li, Wanxiang Zhao\",\"doi\":\"10.1039/d5sc04819b\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Asymmetric remote hydroboration of olefins has emerged as an efficient strategy for the construction of chiral boronic esters. Conventional asymmetric alkene isomerizations rely on directing groups (OH, NR<small><sub>2</sub></small>, carbonyl) for thermodynamic control <em>via</em> (hyper)conjugation, but their use restricts substrate scope and risks β-heteroatom elimination with transition-metal catalysts. We here reported a catalytic asymmetric isomerization/hydroboration of silyl enol ethers under mild conditions, enabling the efficient synthesis of enantioenriched boryl ethers. The chiral borylether products enable efficient access to valuable 1,<em>n</em>-diols and 1,<em>n</em>-amino alcohols, prevalent in bioactive molecules, and facilitate late-stage functionalization of complex architectures. Preliminary mechanistic studies reveal that this reaction involves a nondissociative chain-walking process and that the β-H elimination may contribute to the rate-limiting step.\",\"PeriodicalId\":9909,\"journal\":{\"name\":\"Chemical Science\",\"volume\":\"8 1\",\"pages\":\"\"},\"PeriodicalIF\":7.4000,\"publicationDate\":\"2025-10-03\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Chemical Science\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1039/d5sc04819b\",\"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":"Chemical Science","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d5sc04819b","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Catalytic asymmetric isomerization/hydroboration of silyl enol ethers
Asymmetric remote hydroboration of olefins has emerged as an efficient strategy for the construction of chiral boronic esters. Conventional asymmetric alkene isomerizations rely on directing groups (OH, NR2, carbonyl) for thermodynamic control via (hyper)conjugation, but their use restricts substrate scope and risks β-heteroatom elimination with transition-metal catalysts. We here reported a catalytic asymmetric isomerization/hydroboration of silyl enol ethers under mild conditions, enabling the efficient synthesis of enantioenriched boryl ethers. The chiral borylether products enable efficient access to valuable 1,n-diols and 1,n-amino alcohols, prevalent in bioactive molecules, and facilitate late-stage functionalization of complex architectures. Preliminary mechanistic studies reveal that this reaction involves a nondissociative chain-walking process and that the β-H elimination may contribute to the rate-limiting step.
期刊介绍:
Chemical Science is a journal that encompasses various disciplines within the chemical sciences. Its scope includes publishing ground-breaking research with significant implications for its respective field, as well as appealing to a wider audience in related areas. To be considered for publication, articles must showcase innovative and original advances in their field of study and be presented in a manner that is understandable to scientists from diverse backgrounds. However, the journal generally does not publish highly specialized research.