THE MECHANISM OF ORGANOCUPRATE 1,4-ADDITION REACTIONS WITH ALPHA-BETA-UNSATURATED KETONES - FORMATION OF CUPRATE-ENONE COMPLEXES WITH LITHIUM DIMETHYLCUPRATE

被引：62

作者：

VELLEKOOP, AS ^{[1
]}

SMITH, RAJ ^{[1
]}

机构：

[1] UNIV OTAGO,DEPT CHEM,DUNEDIN,NEW ZEALAND

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1994年 / 116卷 / 07期

关键词：

D O I：

10.1021/ja00086a023

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Colored complexes can be obtained from some enones on addition to ethereal Me(2)CuLi.LiI at -78 degrees C. The unreacted enone can be recovered from these mixtures in high yield by low-temperature protonation. When 2,2,5-trimethyl-4-hexen-3-one was added to Me(2)CuLi.LiI at -80 degrees C, cuprate-olefin and lithium-carbonyl complexes were formed and observed by C-13 NMR. On warming this reaction solution to -55 degrees C, only the lithium-carbonyl complex was detectable which slowly (t(1/2) approximate to 2.5 h) converted into the beta-alkylated enolate. Implications of these observations on the description of the mechanism of the 1,4-addition reaction are presented.

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页码：2902 / 2913

页数：12

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