{"title":"Enantioselective Total Synthesis of Fortalpinoid Q via a TEMPO+BF4–-Mediated Dehydrative Nazarov Cyclization","authors":"Hai-Kang Mao, Qian Wang, Jing Xu","doi":"10.1021/jacs.5c00319","DOIUrl":null,"url":null,"abstract":"The family of <i>Cephalotaxus</i> diterpenoids represents a captivating class of natural products that are of significant interest from both structural and biological perspectives within our community. Here we wish to report a 15-step, enantioselective total synthesis of the <i>Cephalotaxus</i> diterpenoid fortalpinoid Q. Our approach highlights (1) a Jacobsen’s catalytic enantioselective Claisen rearrangement that enabled the single-step formation of two vicinal stereogenic centers, including an all-carbon quaternary center; (2) a mild, oxoammonium salt (TEMPO<sup>+</sup>BF<sub>4</sub><sup>–</sup>)-promoted dehydrative Nazarov cyclization that swiftly forged the crucial cyclopentadiene moiety via an unfunctionalized tertiary divinyl carbinol (TDC) substrate; and (3) a facile aldol-lactonization cascade that ultimately resolved the last obstacle in the synthesis.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"68 1","pages":""},"PeriodicalIF":15.6000,"publicationDate":"2025-03-10","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://doi.org/10.1021/jacs.5c00319","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
Abstract
The family of Cephalotaxus diterpenoids represents a captivating class of natural products that are of significant interest from both structural and biological perspectives within our community. Here we wish to report a 15-step, enantioselective total synthesis of the Cephalotaxus diterpenoid fortalpinoid Q. Our approach highlights (1) a Jacobsen’s catalytic enantioselective Claisen rearrangement that enabled the single-step formation of two vicinal stereogenic centers, including an all-carbon quaternary center; (2) a mild, oxoammonium salt (TEMPO+BF4–)-promoted dehydrative Nazarov cyclization that swiftly forged the crucial cyclopentadiene moiety via an unfunctionalized tertiary divinyl carbinol (TDC) substrate; and (3) a facile aldol-lactonization cascade that ultimately resolved the last obstacle in the synthesis.
期刊介绍：
The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.
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