Synthesis and Desymmetrization of meso Tricyclic Systems Derived from Benzene Oxide
Synthesis and Desymmetrization of meso Tricyclic Systems Derived from Benzene Oxide
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苯氧化物内消旋三环体系的合成与去对称化
DOI：
10.1021/acs.joc.8b00523
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发表时间：
2018
期刊：
影响因子：
--
通讯作者：
Johnson, Jeffrey S.
中科院分区：
文献类型：
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作者：
Matías, Desirée M.;Johnson, Jeffrey S.
来自苯氧化物和N-烷基马来酰亚胺的狄尔斯-阿尔德加合物的臭氧分解导致完全取代的，具有六个连续立构中心的mesobicyclic系统，在用NaBH 4还原后处理时分离为二醇。后处理中的变化允许通过酰亚胺立构中心的双差向异构化分离两种不同的非对映异构体。通过不对称亲核环氧化物开环和酰化反应，得到的mesodiols的去对称化提供了获得高度取代的、对映体富集的稠环的途径。
Ozonolysis of the Diels–Alder adducts derived from benzene oxides andN-alkylmaleimides resulted in fully substituted,mesobicyclic systems bearing six contiguous stereocenters, isolated as diols upon reductive workup with NaBH4. Variation in the workup allowed for isolation of two different diastereoisomers, through double epimerization of the imide stereocenters. Desymmetrization of the resultingmesodiols via asymmetric nucleophilic epoxide opening and acylation reactions provided access to highly substituted, enantioenriched fused rings.