“乌培那胺”ABC环系统的首次合成。

The first synthesis of the ABC-ring system of 'upenamide.

作者信息

Schmidt Jan Peter, Beltrán-Rodil Sandra, Cox Rhona J, McAllister Graeme D, Reid Mark, Taylor Richard J K

机构信息

Department of Chemistry, University of York, York, YO10 5DD, U.K.

出版信息

Org Lett. 2007 Sep 27;9(20):4041-4. doi: 10.1021/ol701772d. Epub 2007 Sep 1.

DOI:10.1021/ol701772d

PMID:17764195

Abstract

The first synthetic route to the spirooxaquinolizidinone core (ABC core) of the macrocyclic marine alkaloid 'upenamide (1) has been developed. All five stereocenters were introduced with complete stereocontrol. The hydroxyl group at C-11 was introduced by a regio- and stereoselective SeO(2)-mediated allylic oxidation. The spirocyclic skeleton was formed by a stannous chloride induced deacetalization-bicyclization procedure. Further stereocenters were introduced by an enzymatic desymmetrization and by incorporation of an (S)-malic acid derived building block.

摘要

大环海洋生物碱“乌彭酰胺（1）”的螺氧喹诺里西啶酮核心（ABC核心）的第一条合成路线已被开发出来。所有五个立体中心都是在完全立体控制下引入的。C-11位的羟基是通过区域和立体选择性的二氧化硒介导的烯丙基氧化引入的。螺环骨架是通过氯化亚锡诱导的脱缩醛化-双环化过程形成的。进一步的立体中心是通过酶促去对称化和引入（S）-苹果酸衍生的结构单元引入的。