碳正离子重排反应合成Cyclocitrinol核心骨架（约稿）
收稿日期: 2014-04-17
修回日期: 2014-05-13
网络出版日期: 2014-05-23
基金资助
国家自然科学青年科学基金(No. 20902098)资助项目.
Synthesis of Cyclocitrinol Skeleton via a Carbocation Rearrangement
Received date: 2014-04-17
Revised date: 2014-05-13
Online published: 2014-05-23
Supported by
Project supported by the National Natural Science Foundation for Young Scientists of China (No. 20902098).
Cyclocitrinol是一类具有独特的桥环结构的天然产物，其桥环核心骨架可由高张力的降蒈烯酮开环制备得到. 以商品化的19-羟基雄甾为原料，通过高烯丙基碳正离子重排反应，高效地合成了降蒈烯酮关键中间体，完成了Cyclocitrinols天然产物的核心骨架的合成.
关键词： 甾体; Mitsunobu反应; Cyclocitrinol; 碳正离子重排
刘涛 , 严语波 , 马海燕 , 丁凯 . 碳正离子重排反应合成Cyclocitrinol核心骨架（约稿）[J]. 有机化学, 2014 , 34(9) : 1793 -1799 . DOI: 10.6023/cjoc201404033
Cyclocitrinol featured a unique bridged bicyclic skeletons, which may be constructed via SmI2-mediated reaction from a highly strained norcarenone. Herein, using commercially available 19-hydroxy-androstane as starting material, the norcarenone intermediate was synthesized via a novel homoallylic carbocation rearrangement, which was transformed into the core of cyclocitrinols.
Key words： steroids; mitsunobu reaction; cyclocitrinol; carbocation rearrangement
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