N-甲氧基-N-酰基氮鎓离子：用于（±）-去甲基氨基FR901483的形式合成

N-methoxy-N-acylnitrenium ions: application to the formal synthesis of (+/-)-desmethylamino FR901483.

作者信息

Wardrop D J, Zhang W

机构信息

Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, Illinois 60607-7061, USA.

出版信息

Org Lett. 2001 Jul 26;3(15):2353-6. doi: 10.1021/ol0161514.

DOI:10.1021/ol0161514

PMID:11463314

Abstract

[reaction: see text] The formal synthesis of (+/-)-desmethylamino FR901483 (2) is described. Construction of the unique azatricyclic skeleton of 2 was accomplished by a sequence which involved (i) preparation of dienone 7 by an N-methoxy-N-acylnitrenium ion-induced spirocyclization, (ii) formation of 2-azabicyclo[3.3.1]nonane 5 by the 6-(pi-exo)-exo-trig radical cyclization of 1,7-enyne 6, and (iii) installation of the C-5 p-methoxybenzyl side chain by Lewis acid-mediated alkylation of silyl enol ether 18.

摘要

[反应：见正文] 描述了(±)-去甲基氨基FR901483（2）的形式合成。2独特的氮杂三环骨架的构建通过以下步骤完成：（i）通过N-甲氧基-N-酰基氮鎓离子诱导的螺环化制备二烯酮7；（ii）通过1,7-烯炔6的6-(π-外向)-外向-三自由基环化形成2-氮杂双环[3.3.1]壬烷5；（iii）通过路易斯酸介导的硅烯醇醚18的烷基化安装C-5对甲氧基苄基侧链。