{"title":"Diastereoselective Synthesis of trans-anti-Hydrophenanthrenes via Ti-mediated Radical Cyclization and Total Synthesis of Kamebanin","authors":"Prof.?Dr. Takahiro Suzuki, Wataru Ikeda, Ayaka Kanno, Prof.?Dr. Kazutada Ikeuchi, Prof.?Dr. Keiji Tanino","doi":"10.1002/chem.202203511","DOIUrl":null,"url":null,"abstract":"<p><i>Ent</i>-kaurenes consist of an ABC-ring based on a <i>trans</i>-<i>anti</i>-hydrophenanthrene skeleton and a D ring with an exomethylene. Highly oxygen-functionalized <i>ent</i>-kauren-15-ones have promising antiinflammatory pharmacological activity. In this study, we developed a novel diastereoselective synthesis of <i>trans</i>-<i>anti</i>-hydrophenanthrenes via a Ti-mediated reductive radical cyclization. We also demonstrated the applicability of this method by developing the first total synthesis of (±)-kamebanin (longest linear sequence; 17 steps, overall yield; 6.5 %). Furthermore, this synthesis provided a formal semi-pinacol rearrangement for the construction of the quaternary carbon at C8 and a novel Thorpe-Ziegler-type reaction for the construction of the D-ring.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":"29 17","pages":""},"PeriodicalIF":3.9000,"publicationDate":"2022-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"1","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemistry - A European Journal","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/chem.202203511","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 1
Abstract
Ent-kaurenes consist of an ABC-ring based on a trans-anti-hydrophenanthrene skeleton and a D ring with an exomethylene. Highly oxygen-functionalized ent-kauren-15-ones have promising antiinflammatory pharmacological activity. In this study, we developed a novel diastereoselective synthesis of trans-anti-hydrophenanthrenes via a Ti-mediated reductive radical cyclization. We also demonstrated the applicability of this method by developing the first total synthesis of (±)-kamebanin (longest linear sequence; 17 steps, overall yield; 6.5 %). Furthermore, this synthesis provided a formal semi-pinacol rearrangement for the construction of the quaternary carbon at C8 and a novel Thorpe-Ziegler-type reaction for the construction of the D-ring.
期刊介绍：
Chemistry—A European Journal is a truly international journal with top quality contributions (2018 ISI Impact Factor: 5.16). It publishes a wide range of outstanding Reviews, Minireviews, Concepts, Full Papers, and Communications from all areas of chemistry and related fields.
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