{"title":"Approach to the Core Structure of Signermycin B","authors":"Dr. Khoa Linh Pham, Prof. Dr. Martin E. Maier","doi":"10.1002/open.202400103","DOIUrl":null,"url":null,"abstract":"<p>Among the natural tetramic acids with a decalinoyl part, signermycin B is unique because it contains a <i>cis</i>-decalin. In this paper, we demonstrate that the <i>cis</i>-decalin section of signermycin B can be accessed by an anionic oxy-Cope rearrangement. The substrate, a tricyclic dienol was prepared by an intramolecular Diels-Alder reaction of a masked <i>ortho</i>-benzoquinone, generated by oxidation of an α-methoxyphenol in presence of <i>cis</i>-2-hexenol. After a superfluous bromine on the cycloadduct was removed, reaction of the tricyclic ketone with isopropenylmagnesium bromide led to the tricyclic trienol that underwent the oxy-Cope rearrangement to a <i>cis</i>-decalinone. While we could show, that introduction of the 4-ethyl substituent (signermycin B numbering) is possible by enolate alkylation, the 4-<i>epi</i>-isomer was formed.</p>","PeriodicalId":9831,"journal":{"name":"ChemistryOpen","volume":null,"pages":null},"PeriodicalIF":2.5000,"publicationDate":"2024-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/open.202400103","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"ChemistryOpen","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/open.202400103","RegionNum":4,"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: 0
Abstract
Among the natural tetramic acids with a decalinoyl part, signermycin B is unique because it contains a cis-decalin. In this paper, we demonstrate that the cis-decalin section of signermycin B can be accessed by an anionic oxy-Cope rearrangement. The substrate, a tricyclic dienol was prepared by an intramolecular Diels-Alder reaction of a masked ortho-benzoquinone, generated by oxidation of an α-methoxyphenol in presence of cis-2-hexenol. After a superfluous bromine on the cycloadduct was removed, reaction of the tricyclic ketone with isopropenylmagnesium bromide led to the tricyclic trienol that underwent the oxy-Cope rearrangement to a cis-decalinone. While we could show, that introduction of the 4-ethyl substituent (signermycin B numbering) is possible by enolate alkylation, the 4-epi-isomer was formed.
在具有癸醛酰基部分的天然四元酸中，符号霉素 B 是独一无二的，因为它含有顺式癸醛。在本文中，我们证明了通过阴离子氧-科普重排可以获得签霉素 B 的顺式癸醛部分。底物是一种三环二烯醇，由α-甲氧基苯酚在顺式-2-己烯醇存在下氧化生成的被掩蔽的邻苯醌通过分子内 Diels-Alder 反应制备而成。除去环加合物上多余的溴后，三环酮与异丙烯基溴化镁反应生成三环三烯醇，三环三烯醇经过氧-科普重排生成顺式癸酮。虽然我们可以证明，通过烯醇烷基化可以引入 4-乙基取代基（符号霉素 B 编号），但形成的是 4-表异构体。
期刊介绍：
ChemistryOpen is a multidisciplinary, gold-road open-access, international forum for the publication of outstanding Reviews, Full Papers, and Communications from all areas of chemistry and related fields. It is co-owned by 16 continental European Chemical Societies, who have banded together in the alliance called ChemPubSoc Europe for the purpose of publishing high-quality journals in the field of chemistry and its border disciplines. As some of the governments of the countries represented in ChemPubSoc Europe have strongly recommended that the research conducted with their funding is freely accessible for all readers (Open Access), ChemPubSoc Europe was concerned that no journal for which the ethical standards were monitored by a chemical society was available for such papers. ChemistryOpen fills this gap.
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号
