双环[7.6]螺环亚胺与丁烯内酯环的合成提供了海洋毒素 13-desMe 螺内酯 C 相对构型的证据。

Synthesis of 7,6-Spirocyclic Imine with Butenolide Ring Provides Evidence for the Relative Configuration of Marine Toxin 13-desMe Spirolide C.

机构信息

Department of Chemistry, Faculty of Science , Osaka University , 1-1 Machikaneyama , Toyonaka , Osaka 560-0043 , Japan.

Research Promotion Institute , Oita University , 1-1 Idaigaoka , Hasama, Yufu , Oita 879-5593 , Japan.

出版信息

Org Lett. 2019 Nov 15;21(22):8970-8975. doi: 10.1021/acs.orglett.9b03373. Epub 2019 Oct 30.

DOI:10.1021/acs.orglett.9b03373

PMID:31663765

Abstract

Efficient synthesis of the partial structure of marine toxin 13-desMe spirolide C was achieved via the selective Diels-Alder reaction and C-C bond formation with the use of a silatrane substituent and the subsequent facile formation of a γ-butenolide ring. The comparison of NMR data between the synthesized diastereomers and the natural product strongly suggested that the relative configuration at the C4 position was configuration with respect to the 7,6-spirocycle.

摘要

通过使用硅氮烷取代基的选择性 Diels-Alder 反应和 C-C 键形成，以及随后易于形成 γ-丁烯内酯环，实现了海洋毒素 13-desMe 螺旋内酯 C 的部分结构的高效合成。合成的非对映异构体与天然产物的 NMR 数据的比较强烈表明，C4 位的相对构型是相对于 7,6-螺环的构型。