Use of epoxidation and epoxide opening reactions for the synthesis of highly functionalized 1-oxaspiro[4.5]decan-2-ones and related compounds
Use of epoxidation and epoxide opening reactions for the synthesis of highly functionalized 1-oxaspiro[4.5]decan-2-ones and related compounds
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DOI：
10.1016/j.tet.2003.08.010
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发表时间：
2003-09-29
期刊：
影响因子：
2.1
通讯作者：
Maier, ME
中科院分区：
文献类型：
--
作者：
Eipert, M;Maichle-Mössmer, C;Maier, ME
3-（6-羟基环己-1-烯-1-基）丙酸乙酯（11）的环氧化提供顺式环氧化物12。通过引发螯合控制的环氧化物开环，可以获得三醇衍生物13和14或螺内酯25。从溴化物26和27中消除HBr产生螺环环己烯酮28和29。双键的环氧化以非对映选择性方式发生，分别得到环氧化物30和31。用LiBr/AcOH处理环氧化物31得到溴代醇38。以旋转木马的方式，38通过消除、环氧化和环氧化物开环在环己烷环上进一步官能化，得到溴代醇43。在这些研究期间产生的其他环己烷衍生物包括环己烯酮19和环己二醇23。此外，螺内酯29的烯醇化叠氮化以非对映选择性方式进行，提供α-叠氮基内酯32。(C)2003 Elsevier Ltd.保留所有权利。
Epoxidation of ethyl 3-(6-hydroxycyclohex-1-en-1-yl)propanoate (11) provided the syn epoxide 12. By invoking chelation controlled epoxide opening the triol derivatives 13 and 14 or the spiro lactone 25 could be obtained. Elimination of HBr from the bromides 26 and 27 produced the spiro cyclohexenones 28 and 29. Epoxidation of the double bond occurred in a diastereoselective manner to give epoxides 30 and 31, respectively. Treatment of the epoxide 31 with LiBr/AcOH gave the bromo hydrin 38. In a merry go round' fashion 38 was further functionalized on the cyclohexane ring by elimination, epoxidation, and epoxide opening resulting in the bromo hydrin 43. Other cyclohexane derivatives that were produced during these studies include the cyclohexenone 19 and the cyclohexanediol 23. In addition, enolate azidation of the spiro lactone 29 proceeded in a diastereoselective manner providing the a-azido lactone 32. (C) 2003 Elsevier Ltd. All rights reserved.