{"title":"人工手性三核锌催化剂:酮类不对称硼氢化反应的设计、自组装和空前效率","authors":"Jingxi He, , , Shuxin Jiang, , , Yu Qiu, , , Yingchao Liu, , , Kuiling Ding*, , and , Xiaoming Wang*, ","doi":"10.1021/acscentsci.5c01067","DOIUrl":null,"url":null,"abstract":"<p >The development of artificial catalysts with efficiency that can rival those of Nature’s enzymes represents one of the foremost yet challenging goals in homogeneous metal catalysis. Inspired by the exceptional performance of metalloenzymes, the design and development of highly efficient bi/multinuclear catalysts via judicious ligand design, by taking advantage of the cooperative action of the proximal catalytic sites, has attracted great attention. Herein, we report the self-assembly of a chiral hexadentate BINOL-dipyox ligand with zinc acetate into a well-defined trinuclear zinc complex, which demonstrated ultrahigh catalytic productivity in the enantioselective hydroboration of ketones with an unprecedented turnover number (TON) of 19,400 at an extremely low catalyst loading (0.005 mol %). Mechanistic investigations reveal that a cooperative Lewis acid activation mode is operating in the catalytic process, hence, underscoring the unique advantages of the trinuclear architecture.</p><p >This work reports the rational design and self-assembly of an artificial chiral trinuclear zinc catalyst, which exhibits exceptional efficiency in enantioselective ketone hydroboration.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 9","pages":"1773–1783"},"PeriodicalIF":10.4000,"publicationDate":"2025-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acscentsci.5c01067","citationCount":"0","resultStr":"{\"title\":\"Artificial Chiral Trinuclear Zn Catalysts: Design, Self-Assembly and Unprecedented Efficiency in Asymmetric Hydroboration of Ketones\",\"authors\":\"Jingxi He, , , Shuxin Jiang, , , Yu Qiu, , , Yingchao Liu, , , Kuiling Ding*, , and , Xiaoming Wang*, \",\"doi\":\"10.1021/acscentsci.5c01067\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >The development of artificial catalysts with efficiency that can rival those of Nature’s enzymes represents one of the foremost yet challenging goals in homogeneous metal catalysis. Inspired by the exceptional performance of metalloenzymes, the design and development of highly efficient bi/multinuclear catalysts via judicious ligand design, by taking advantage of the cooperative action of the proximal catalytic sites, has attracted great attention. Herein, we report the self-assembly of a chiral hexadentate BINOL-dipyox ligand with zinc acetate into a well-defined trinuclear zinc complex, which demonstrated ultrahigh catalytic productivity in the enantioselective hydroboration of ketones with an unprecedented turnover number (TON) of 19,400 at an extremely low catalyst loading (0.005 mol %). Mechanistic investigations reveal that a cooperative Lewis acid activation mode is operating in the catalytic process, hence, underscoring the unique advantages of the trinuclear architecture.</p><p >This work reports the rational design and self-assembly of an artificial chiral trinuclear zinc catalyst, which exhibits exceptional efficiency in enantioselective ketone hydroboration.</p>\",\"PeriodicalId\":10,\"journal\":{\"name\":\"ACS Central Science\",\"volume\":\"11 9\",\"pages\":\"1773–1783\"},\"PeriodicalIF\":10.4000,\"publicationDate\":\"2025-08-12\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.acs.org/doi/pdf/10.1021/acscentsci.5c01067\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ACS Central Science\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acscentsci.5c01067\",\"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":"ACS Central Science","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acscentsci.5c01067","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Artificial Chiral Trinuclear Zn Catalysts: Design, Self-Assembly and Unprecedented Efficiency in Asymmetric Hydroboration of Ketones
The development of artificial catalysts with efficiency that can rival those of Nature’s enzymes represents one of the foremost yet challenging goals in homogeneous metal catalysis. Inspired by the exceptional performance of metalloenzymes, the design and development of highly efficient bi/multinuclear catalysts via judicious ligand design, by taking advantage of the cooperative action of the proximal catalytic sites, has attracted great attention. Herein, we report the self-assembly of a chiral hexadentate BINOL-dipyox ligand with zinc acetate into a well-defined trinuclear zinc complex, which demonstrated ultrahigh catalytic productivity in the enantioselective hydroboration of ketones with an unprecedented turnover number (TON) of 19,400 at an extremely low catalyst loading (0.005 mol %). Mechanistic investigations reveal that a cooperative Lewis acid activation mode is operating in the catalytic process, hence, underscoring the unique advantages of the trinuclear architecture.
This work reports the rational design and self-assembly of an artificial chiral trinuclear zinc catalyst, which exhibits exceptional efficiency in enantioselective ketone hydroboration.
期刊介绍:
ACS Central Science publishes significant primary reports on research in chemistry and allied fields where chemical approaches are pivotal. As the first fully open-access journal by the American Chemical Society, it covers compelling and important contributions to the broad chemistry and scientific community. "Central science," a term popularized nearly 40 years ago, emphasizes chemistry's central role in connecting physical and life sciences, and fundamental sciences with applied disciplines like medicine and engineering. The journal focuses on exceptional quality articles, addressing advances in fundamental chemistry and interdisciplinary research.