A formal total synthesis of (+/-)-halichlorine and (+/-)-pinnaic acid.
A formal total synthesis of (+/-)-halichlorine and (+/-)-pinnaic acid.
复制标题
DOI：
10.1021/ol0301431
复制
发表时间：
2004-02
期刊：
影响因子：
5.2
通讯作者：
Yosuke Matsumura;S. Aoyagi;C. Kibayashi
中科院分区：
文献类型：
--
作者：
Yosuke Matsumura;S. Aoyagi;C. Kibayashi
[反应：见正文] 已经开发了一种用于制备Danishefsky中间体的立体控制方法，以氮杂螺双环酮作为共同前体，代表了(+/-)-卤氯和(+/-)-蒎酸的正式全合成。该方法涉及构建具有适当立体化学的 1,7-二取代 6-氮杂螺[4.5]癸烷，该立体化学通过烯烃氢化、随后螺三环内酰胺的 C-甲基化以及涉及使用三氟甲磺酸甲酯和 RCM 进行内酰胺开环以形成氮杂螺三环喹里西啶骨架的后续过程来建立。
[reaction: see text] A stereocontrolled approach for the preparation of the Danishefsky intermediates has been developed starting with the azaspirobicyclic ketone as a common precursor, representing a formal total synthesis of (+/-)-halichlorine and (+/-)-pinnaic acid. This approach involves the construction of the 1,7-disubstituted 6-azaspiro[4.5]decane with the proper stereochemistry established by olefin hydrogenation followed by C-methylation of the spirotricyclic lactam and the subsequent processes involving lactam ring-opening using methyl triflate and RCM to form the azaspirotricyclic quinolizidine skeleton.