对苯甘氨醇衍生的不饱和δ-内酰胺的共轭加成反应。乌来因生物碱的对映选择性合成。

Conjugate additions to phenylglycinol-derived unsaturated delta-lactams. Enantioselective synthesis of uleine alkaloids.

作者信息

Amat Mercedes, Pérez Maria, Llor Núria, Escolano Carmen, Luque F Javier, Molins Elies, Bosch Joan

机构信息

Laboratory of Organic Chemistry and Department of Physical Chemistry, Faculty of Pharmacy, University of Barcelona, 08028 Barcelona, Spain.

出版信息

J Org Chem. 2004 Dec 10;69(25):8681-93. doi: 10.1021/jo0487101.

DOI:10.1021/jo0487101

PMID:15575744

Abstract

The stereochemical outcome of the conjugate addition of a variety of stabilized nucleophiles (2-indoleacetic enolates and sulfur-stabilized anions) to the phenylglycinol-derived unsaturated lactams trans-2, cis-2, and its 8-ethyl-substituted analogue 10 is studied. The factors governing the exo or endo facial stereoselectivity are discussed. This methodology provides short synthetic routes to either cis- or trans-3,4-disubstituted enantiopure piperidines as well as efficient routes for the enantioselective construction of the tetracyclic ring system of uleine alkaloids, both in the normal and 20-epi series. The formal total synthesis of several alkaloids of this group is reported.

摘要

研究了多种稳定亲核试剂（2-吲哚乙酸烯醇盐和硫稳定阴离子）对苯基甘氨醇衍生的不饱和内酰胺反式-2、顺式-2及其8-乙基取代类似物10进行共轭加成的立体化学结果。讨论了控制外型或内型面立体选择性的因素。该方法为顺式或反式-3,4-二取代对映体纯哌啶提供了短合成路线，也为乌灵生物碱四环环系在正常系列和20-表系列中的对映选择性构建提供了有效路线。报道了该类几种生物碱的形式全合成。