二异四萜 Oxyphyllin A/Belchinoid A 的全合成

IF 1.5 4区医学 Q4 CHEMISTRY, MEDICINAL

Chemical & pharmaceutical bulletin Pub Date : 2024-07-23 DOI:10.1248/cpb.c24-00332

Koichiro Ota, Naoya Kashima, Haruhiko Fukaya, Shinnosuke Okazaki, Hiroaki Miyaoka

{"title":"二异四萜 Oxyphyllin A/Belchinoid A 的全合成","authors":"Koichiro Ota, Naoya Kashima, Haruhiko Fukaya, Shinnosuke Okazaki, Hiroaki Miyaoka","doi":"10.1248/cpb.c24-00332","DOIUrl":null,"url":null,"abstract":"Here, we report the first synthesis of oxyphyllin A/belchinoid A, a 7,9-seco-8,12-dinor-guaiane sesquiterpene whose isolation was reported independently by two groups in 2023. This synthesis utilizes a key sequential sulfone-mediated intermolecular alkylation/5-endo-tet cyclization reaction to establish the C1, C4, C5 stereocenters. Subsequent transformations, including regio- and stereoselective hydride addition-based desulfonylation via a π–allyl palladium complex and the Wittig reaction with a stable phosphonium ylide, facilitated the synthesis of oxyphyllin A/belchinoid A.\n\n<img alt=\"\" src=\"https://www.jstage.jst.go.jp/pub/cpb/72/7/72_c24-00332/figure/72_c24-00332.png\"/>\nFullsize Image","PeriodicalId":9773,"journal":{"name":"Chemical & pharmaceutical bulletin","volume":null,"pages":null},"PeriodicalIF":1.5000,"publicationDate":"2024-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Total Synthesis of Dinorsesquiterpenoid Oxyphyllin A/Belchinoid A\",\"authors\":\"Koichiro Ota, Naoya Kashima, Haruhiko Fukaya, Shinnosuke Okazaki, Hiroaki Miyaoka\",\"doi\":\"10.1248/cpb.c24-00332\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Here, we report the first synthesis of oxyphyllin A/belchinoid A, a 7,9-seco-8,12-dinor-guaiane sesquiterpene whose isolation was reported independently by two groups in 2023. This synthesis utilizes a key sequential sulfone-mediated intermolecular alkylation/5-endo-tet cyclization reaction to establish the C1, C4, C5 stereocenters. Subsequent transformations, including regio- and stereoselective hydride addition-based desulfonylation via a π–allyl palladium complex and the Wittig reaction with a stable phosphonium ylide, facilitated the synthesis of oxyphyllin A/belchinoid A.\\n\\n<img alt=\\\"\\\" src=\\\"https://www.jstage.jst.go.jp/pub/cpb/72/7/72_c24-00332/figure/72_c24-00332.png\\\"/>\\nFullsize Image\",\"PeriodicalId\":9773,\"journal\":{\"name\":\"Chemical & pharmaceutical bulletin\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":1.5000,\"publicationDate\":\"2024-07-23\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Chemical & pharmaceutical bulletin\",\"FirstCategoryId\":\"3\",\"ListUrlMain\":\"https://doi.org/10.1248/cpb.c24-00332\",\"RegionNum\":4,\"RegionCategory\":\"医学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"CHEMISTRY, MEDICINAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemical & pharmaceutical bulletin","FirstCategoryId":"3","ListUrlMain":"https://doi.org/10.1248/cpb.c24-00332","RegionNum":4,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CHEMISTRY, MEDICINAL","Score":null,"Total":0}

引用次数: 0

摘要

在此，我们首次报道了羟基斑蝥素 A/贝壳杉烯 A 的合成，这是一种 7,9-seco-8,12-dinor-guaiane 倍半萜，其分离工作由两个研究小组于 2023 年独立完成。该合成利用了一个关键的顺序砜介导的分子间烷基化/5-内向四环化反应来建立 C1、C4、C5 立体中心。随后的转化，包括通过π-烯丙基钯络合物进行的基于氢化物加成的区域和立体选择性脱磺化反应，以及与稳定的膦酰亚胺进行的 Wittig 反应，促进了氧基斑蝥素/斑蝥素 A 的合成。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

查看原文本刊更多论文

Total Synthesis of Dinorsesquiterpenoid Oxyphyllin A/Belchinoid A

Here, we report the first synthesis of oxyphyllin A/belchinoid A, a 7,9-seco-8,12-dinor-guaiane sesquiterpene whose isolation was reported independently by two groups in 2023. This synthesis utilizes a key sequential sulfone-mediated intermolecular alkylation/5-endo-tet cyclization reaction to establish the C1, C4, C5 stereocenters. Subsequent transformations, including regio- and stereoselective hydride addition-based desulfonylation via a π–allyl palladium complex and the Wittig reaction with a stable phosphonium ylide, facilitated the synthesis of oxyphyllin A/belchinoid A.

Fullsize Image

求助全文

通过发布文献求助，成功后即可免费获取论文全文。去求助

来源期刊

Chemical & pharmaceutical bulletin 医学-化学综合

CiteScore

3.20

自引率

5.90%

发文量

132

审稿时长

1.7 months

期刊介绍： The CPB covers various chemical topics in the pharmaceutical and health sciences fields dealing with biologically active compounds, natural products, and medicines, while BPB deals with a wide range of biological topics in the pharmaceutical and health sciences fields including scientific research from basic to clinical studies. For details of their respective scopes, please refer to the submission topic categories below. Topics: Organic chemistry In silico science Inorganic chemistry Pharmacognosy Health statistics Forensic science Biochemistry Pharmacology Pharmaceutical care and science Medicinal chemistry Analytical chemistry Physical pharmacy Natural product chemistry Toxicology Environmental science Molecular and cellular biology Biopharmacy and pharmacokinetics Pharmaceutical education Chemical biology Physical chemistry Pharmaceutical engineering Epidemiology Hygiene Regulatory science Immunology and microbiology Clinical pharmacy Miscellaneous.