Spirodiepoxides: synthesis of epoxomicinoids.
Spirodiepoxides: synthesis of epoxomicinoids.
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Spirodiepides：环氧类霉素的合成。
DOI：
10.1021/jo901320f
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发表时间：
2009
期刊：
影响因子：
--
通讯作者：
Williams,LawrenceJ
中科院分区：
文献类型：
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作者：
Zhang,Yue;Cusick,JosephR;Ghosh,Partha;Shangguan,Ning;Katukojvala,Sreenivas;Inghrim,Jennifer;Emge,ThomasJ;Williams,LawrenceJ
合成了三种密切相关的环氧霉素类似物。丙二烯衍生的螺二环氧化物是关键中间体。螺双环氧化物的形成和立体化学依赖于溶剂，氧化剂和丙二烯结构进行了编目。在氯仿中，1，3-二取代和三取代联烯与二甲基二环氧乙烷的第一次环氧化的面选择性>20：1。对于立体异构的联烯，二次氧化的面选择性主要取决于联烯的结构，其次取决于溶剂和氧化剂。对于所评价的无环体系，该比率高达8：1。一个构象模型是先进的占这些意见。
Three closely related analogues of epoxomicin have been synthesized. Allene-derived spirodiepoxides were key intermediates. Spirodiepoxide formation and stereochemical dependence on solvent, oxidant, and allene structure were cataloged. The facial selectivity of the first epoxidation of 1,3-disubstituted and trisubstituted allenes was found to be >20:1 with dimethyldioxirane in chloroform. For stereogenic allenes, the facial selectivity of the second oxidation is dependent primarily on allene structure and secondarily on solvent and oxidant. For the acyclic systems evaluated this ratio was as high as 8:1. A conformational model is advanced to account for these observations.