alpha,beta-Unsaturated nitriles: Stereoselective conjugate addition reactions

被引：39

作者：

Fleming, FF

Hussain, Z

Weaver, D

Norman, RE

机构：

[1] Department of Chemistry, Duquesne University, Pittsburgh

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1997年 / 62卷 / 05期

关键词：

CARBONYL-COMPOUNDS; TRANS-1,3-DITHIANE 1,3-DIOXIDE; QUINOLIZIDINE ALKALOIDS; ORGANOCOPPER REAGENTS; 1,3-DITHIANE 1-OXIDES; KETONES; 2-LITHIO-1,3-DITHIANES; 1,4-ADDITION; INDOLIZIDINE; CHEMISTRY;

D O I：

10.1021/jo9619894

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Dithiane anions undergo intramolecular conjugate additions with alpha,beta-unsaturated nitriles when a dithiane anion is tethered to N-1 of the 3-cyano-1,4,5,6-tetrahydropyridine nucleus. 3-Cyano-1-[2-(1,3-dithianyl-2-yl)ethyl]-1,4,5,6-tetrahydropyridine (1a) and the one-carbon homologue 1b cyclize in the presence of 12-crown-4 to generate indolizidine 3 and quinolizidine 9, in which the nitrile group exhibits a strong, thermodynamic preference for the axial orientation. Oxidation of Ib provides dithiane S-oxide 10 that undergoes a highly stereoselective conjugate addition to provide crystalline quinolizidine 13. The X-ray structure of 13 is reported and corroborates our ''peg-in-a-pocket'' principle for stereoselective conjugate additions with alpha,beta-unsaturated nitriles.

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页码：1305 / 1309

页数：5

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