通过酰胺基丙烯醛环加成反应全合成（±）-柄海鞘胺

Total synthesis of (+/-)-lepadiformine via an amidoacrolein cycloaddition.

作者信息

Greshock T J, Funk R L

机构信息

Department of Chemistry, Pennsylvania State University, University Park, Pennsylvania 16802, USA.

出版信息

Org Lett. 2001 Nov 1;3(22):3511-4. doi: 10.1021/ol0165903.

DOI:10.1021/ol0165903

PMID:11678695

Abstract

[reaction: see text]. The total synthesis of the cytotoxin lepadiformine is described. The intermolecular cycloaddition of a 2-amidoacrolein with the dimethyl acetal of 4,6-heptadienal gave a cycloadduct that was strategically functionalized for elaboration of the tricyclic ring system. These steps include a diastereoselective addition of an organoytterbium reagent to an aldehyde, cyclization to the trans-perhydroquinoline substructure via a Mitsunobu reaction, and an iodine-promoted amine cyclization with an alkene to introduce the pyrrolidine ring.

摘要

[反应：见正文]。描述了细胞毒素lepadiformine的全合成。2-氨基丙烯醛与4,6-庚二烯醛的二甲基缩醛进行分子间环加成反应，得到一种环加成产物，该产物经过策略性官能团化以构建三环体系。这些步骤包括将有机镱试剂非对映选择性地加成到醛上，通过 Mitsunobu 反应环化形成反式全氢喹啉亚结构，以及用碘促进胺与烯烃环化以引入吡咯烷环。