Towards an understanding of the conjugate addition of organolithium reagents to α,β-unsaturated ketones:: the isolation and solid-state structure of a monomeric lithium aluminate with very short agostic Li•••HC interactions

被引:52
作者
Clegg, W
Lamb, E
Liddle, ST
Snaith, R
Wheatley, AEH
机构
[1] Univ Cambridge, Dept Chem, Cambridge CB2 1EW, England
[2] Univ Newcastle Upon Tyne, Dept Chem, Newcastle Upon Tyne NE1 7RU, Tyne & Wear, England
基金
英国工程与自然科学研究理事会;
关键词
aluminium; alpha; beta-unsaturated ketone; conjugate addition; lithium; solid-state structure;
D O I
10.1016/S0022-328X(98)00876-6
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Reaction of methylaluminium bis(2,6-di-tert-butyl-4-methylphenoxide) (MAD), I, with alkyllithium reagents, R'Li (R' = Me, n-Bu or t-Bu), yields the solvent-dependent products lithium bis(2,6-di-tert-butyl-4-methylphenoxide) complex, 2 THF, lithium dimethylbis(2,6-di-tert-butyl-4-methylphenoxide)aluminate 3, a new type of lithium aluminate in which the lithium centre is stabilised by very short agostic Li ... H(t-Bu) interactions, and tris(alkyl)aluminium. The observation of these products suggests an explanation for the tendency of alpha,beta-unsaturated ketones to undergo conjugate (rather than 1,2-) addition in the presence of MAD and organolithium reagents. (C) 1999 Elsevier Science S.A. All rights reserved.
引用
收藏
页码:305 / 312
页数:8
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