Unsaturated oxo-nitriles: Stereoselective, chelation-controlled conjugate additions

被引：13

作者：

Fleming, FF ^{[1
]}

Guo, JP

Wang, QZ

Weaver, D

机构：

[1] Duquesne Univ, Dept Chem & Biochem, Pittsburgh, PA 15282 USA

[2] Bristol Myers Squibb Co, Syracuse, NY 13221 USA

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1999年 / 64卷 / 23期

关键词：

D O I：

10.1021/jo9909709

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Addition of Grignard reagents to the unsaturated oxo-nitrile 10 (4-hydroxy-4-methyl-6-oxocyclohex-1-enecarbonitrile) provides conjugate addition products with virtually complete stereocontrol. Mechanistic evidence supports a chelation-controlled conjugate addition via alkylmagnesium alkoxide inter mediates. Diverse Grignard reagents having sp(3)-, sp(2)-, and sp-hybridized carbons react with comparable efficiency, with even sterically demanding nucleophiles adding with complete stereocontrol. Unsaturated oxo-nitriles that are incapable of chelation afford diastereomeric conjugate addition products through an unusual boatlike transition state. Collectively, these reactions illustrate the complementary stereoselectivity of chelation-controlled conjugate additions to hydroxylated, unsaturated oxo-nitriles and stereoelectronically controlled conjugate additions to enones.

引用

页码：8568 / 8575

页数：8

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