Some observations on the mechanism of diorganocuprate 1,4-addition reactions with alpha,beta-unsaturated ketones: Effects of diethyl ether in reactions of butylcoppers in toluene

被引:23
作者
Kingsbury, CL [1 ]
Smith, RAJ [1 ]
机构
[1] UNIV OTAGO,DEPT CHEM,DUNEDIN,NEW ZEALAND
关键词
D O I
10.1021/jo970316y
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Mixtures of butyllithium and copper iodide prepared in toluene react with alpha,beta-unsaturated ketones predominantly in a 1,2-fashion. Addition of 2 equiv of diethyl ether to the system results in a dramatic preference for the 1,4-product, as found normally with diorganocuprates in ethereal solvents. These results are in accordance with the theoretical predictions that a suitable ligand is required to facilitate the stabilization of a formally copper(III) reaction intermediate on the 1,4-addition mechanistic pathway.
引用
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页码:4629 / 4634
页数:6
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