{"title":"作为惰性键活化和还原不饱和体系的强效还原光催化剂的双乙醇酸盐","authors":"Can Liu, Yan Zhang, Rui Shang","doi":"10.1016/j.chempr.2024.10.026","DOIUrl":null,"url":null,"abstract":"Phenolates are increasingly studied as photocatalysts because of their abundance and easy accessibility. However, their potential as potent and broadly applicable reducing photoredox catalysts is hindered by the high electronegativity of oxygen and the reactivity of phenoxy radicals. Herein, we discovered that renowned 1,1′-Bi-2-naphtholate derivatives (BINOLates) are potent reducing photocatalysts. These catalysts are effective for the activation of inert bonds and the reduction of unsaturated bonds, including selective CF activation of activated –CF<sub>3</sub>,–CF<sub>2</sub>H, –C<sub>2</sub>F<sub>5</sub>, and aryl fluoride, activation of alkyl and aryl chlorides, detosylation, Birch reduction, and alkene reduction, demonstrating potent reducing ability and catalytic versatility. Defluoroalkylation using PhCF<sub>3</sub> as a limiting reagent, a challenging substrate for reported catalysts, proceeded smoothly. BINOLates were applicable as photoredox catalysts even under green light. This work introduces a new catalytic application for the renowned BINOLates, suggesting the potential for future expansion of their applications in the realm of photocatalysis.","PeriodicalId":268,"journal":{"name":"Chem","volume":"20 1","pages":""},"PeriodicalIF":19.1000,"publicationDate":"2024-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"BINOLates as potent reducing photocatalysts for inert bond activation and reduction of unsaturated systems\",\"authors\":\"Can Liu, Yan Zhang, Rui Shang\",\"doi\":\"10.1016/j.chempr.2024.10.026\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Phenolates are increasingly studied as photocatalysts because of their abundance and easy accessibility. However, their potential as potent and broadly applicable reducing photoredox catalysts is hindered by the high electronegativity of oxygen and the reactivity of phenoxy radicals. Herein, we discovered that renowned 1,1′-Bi-2-naphtholate derivatives (BINOLates) are potent reducing photocatalysts. These catalysts are effective for the activation of inert bonds and the reduction of unsaturated bonds, including selective CF activation of activated –CF<sub>3</sub>,–CF<sub>2</sub>H, –C<sub>2</sub>F<sub>5</sub>, and aryl fluoride, activation of alkyl and aryl chlorides, detosylation, Birch reduction, and alkene reduction, demonstrating potent reducing ability and catalytic versatility. Defluoroalkylation using PhCF<sub>3</sub> as a limiting reagent, a challenging substrate for reported catalysts, proceeded smoothly. BINOLates were applicable as photoredox catalysts even under green light. This work introduces a new catalytic application for the renowned BINOLates, suggesting the potential for future expansion of their applications in the realm of photocatalysis.\",\"PeriodicalId\":268,\"journal\":{\"name\":\"Chem\",\"volume\":\"20 1\",\"pages\":\"\"},\"PeriodicalIF\":19.1000,\"publicationDate\":\"2024-12-11\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Chem\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1016/j.chempr.2024.10.026\",\"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":"Chem","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1016/j.chempr.2024.10.026","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
BINOLates as potent reducing photocatalysts for inert bond activation and reduction of unsaturated systems
Phenolates are increasingly studied as photocatalysts because of their abundance and easy accessibility. However, their potential as potent and broadly applicable reducing photoredox catalysts is hindered by the high electronegativity of oxygen and the reactivity of phenoxy radicals. Herein, we discovered that renowned 1,1′-Bi-2-naphtholate derivatives (BINOLates) are potent reducing photocatalysts. These catalysts are effective for the activation of inert bonds and the reduction of unsaturated bonds, including selective CF activation of activated –CF3,–CF2H, –C2F5, and aryl fluoride, activation of alkyl and aryl chlorides, detosylation, Birch reduction, and alkene reduction, demonstrating potent reducing ability and catalytic versatility. Defluoroalkylation using PhCF3 as a limiting reagent, a challenging substrate for reported catalysts, proceeded smoothly. BINOLates were applicable as photoredox catalysts even under green light. This work introduces a new catalytic application for the renowned BINOLates, suggesting the potential for future expansion of their applications in the realm of photocatalysis.
期刊介绍:
Chem, affiliated with Cell as its sister journal, serves as a platform for groundbreaking research and illustrates how fundamental inquiries in chemistry and its related fields can contribute to addressing future global challenges. It was established in 2016, and is currently edited by Robert Eagling.