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引用次数: 0
摘要
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。
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.
期刊介绍:
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