通过多不饱和环氧化物环化全合成（±）-11α-羟基孕酮

Total synthesis of (+/-)-11 alpha-hydroxyprogesterone by cyclization of a polyunsaturated epoxide.

作者信息

van Tamelen E E, Faler D L

出版信息

Proc Natl Acad Sci U S A. 1985 Apr;82(7):1879-80. doi: 10.1073/pnas.82.7.1879.

DOI:10.1073/pnas.82.7.1879

原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC397433/

Abstract

The total synthesis of a typical 11-hydroxylated steroid, (+/-)-11 alpha-hydroxyprogesterone, was achieved by picric acid-catalyzed tricyclization of a polyunsaturated epoxide appropriately substituted with ketal, hydroxyl, and acetylenic units. This epoxide was prepared by a multistage sequence featuring two successive alkylations of intermediary, monocyclic sulfones. The first sulfone intermediate was obtained by means of a short sequence starting from levulinic acid and diethyl succinate and involving a selective cyclization reaction.

摘要

通过苦味酸催化的多不饱和环氧化物的三环化反应，成功实现了典型的11-羟基化甾体（±）-11α-羟基孕酮的全合成，该多不饱和环氧化物被缩酮、羟基和炔基单元适当取代。该环氧化物是通过一个多步序列制备的，该序列的特点是中间体单环砜的两次连续烷基化反应。第一个砜中间体是通过一个短序列从乙酰丙酸和丁二酸二乙酯开始制备的，该序列涉及一个选择性环化反应。

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本文引用的文献

1

Letter: Biomimetic polyene cyclizations. Asymmetric induction by a chiral center remote from the initiating cationic center. 11alpha-methylprogesterone.信函：仿生多烯环化反应。远离起始阳离子中心的手性中心的不对称诱导作用。11α-甲基孕酮。

J Am Chem Soc. 1976 Feb 18;98(4):1038-9. doi: 10.1021/ja00420a040.

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