Electrochemical synthesis of chroman and euglobal skeletons via cycloaddition reaction of o-quinone methides and alkenes
Electrochemical synthesis of chroman and euglobal skeletons via cycloaddition reaction of o-quinone methides and alkenes
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DOI：
10.1039/p19960001435
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发表时间：
1996-06-21
期刊：
影响因子：
--
通讯作者：
Tada, M
中科院分区：
文献类型：
--
作者：
Chiba, K;Sonoyama, J;Tada, M
通过电化学氧化原位生成的萜烯和邻苯二酚甲醚的分子间环加成反应合成了超球形骨架。在由正己烷-高氯酸锂/硝基甲烷组成的两相反应介质中，2-[1-(丙基亚磺基)烷基]苯酚被选择性地氧化成相应的不稳定邻苯二酚亚甲基。这些中间体被未活化的烯烃或易氧化的萜烯原位捕获，形成各种色曼和螺色曼，包括真球状骨架。特别是，在β-蒎烯存在下，具有β-水芹烯部分的真全球IIb骨架是通过β-蒎烯的骨架重排进行环加成反应形成的。
Euglobal skeletons were synthesized by the intermolecular cycloaddition reaction of terpenes and o-quinone methides generated in situ by electrochemical oxidation. In a two-phase reaction medium composed of hexane-lithium perchlorate/nitromethane, 2-[1-(propylsulfanyl)alkyl] phenols were selectively oxidized to give the corresponding unstable o-quinone methides. These intermediates were trapped in situ by unactivated alkenes or easily oxidizable terpenes to form varied chromans and spirochromans including euglobal skeletons. In particular, in the presence of beta-pinene, the euglobal IIb skeleton, which possesses a beta-phellandrene moiety, is formed by the cycloaddition via skeletal rearrangement of beta-pinene.