Effect of InCl 3 on the addition of Grignard reagents to α,β-unsaturated carbonyl compounds
作者:Brian G. Kelly、Declan G. Gilheany
DOI:10.1016/s0040-4039(01)02263-8
日期:2002.1
Control of 1,2- versus 1,4-addition of organometallic reagents to enones remains a long-standing problem. There is still no satisfactory 1,2-directing agent comparable to the 1,4-directing effect of copper salts. We report that the presence of just 5 mol% indium(III) chloride can significantly alter the amount of 1,2-product formed in these reactions.
The conjugateaddition of organolithium reagent to α, β-unsaturatedketone has been accomplished with methylaluminum bis(2, 6-di-tert-butyl-4-alkylphenoxide) (MAD and MAT). Here combination of alkyllithium and MAD (or MAT) constitutes an amphiphilic system that allows to exhibit unusual selectivity in the alkylation of enones with alkyllithium.
Amphiphilic reactions by means of exceptionally bulky organoaluminum reagents. Rational approach for obtaining unusual equatorial, anti-Cram, and 1,4 selectivity in carbonyl alkylation