Copper-catalyzed asymmetric conjugate addition of trialkylaluminium reagents to trisubstituted enones: Construction of chiral quaternary centers

被引:125
作者
Vuagnoux-d'Augustin, Magali [1 ]
Alexakis, Alexandre [1 ]
机构
[1] Univ Geneva, Dept Chim Organ, CH-1211 Geneva, Switzerland
关键词
aluminium; asymmetric catalysis; conjugate addition; copper; phosphoramidite ligands;
D O I
10.1002/chem.200701001
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Me3Al, Et3Al, and vinylalane species undergo enantioselective conjugate addition to a wide range of 2- or 3-substituted enones (cyclopent-2-enones, cyclohex-2-enones, 3-methyl cyclohept-2-enone) in the presence of catalytic amount of copper salt (copper thiophene carboxylate, [Cu(CH3CN)(4)]BF4 or [CuOTf](2)center dot C6H6) and tropos-phosphoramidite-based ligand. Thus, chiral quaternary centers can be built, with up to 98% ee after rigorous optimization of experimental conditions. It was shown that the main important parameter was the order of the introduction of the reagents. 'nen, the generated enantioenriched aluminium, enolates and the chiral conjugate adducts were functionalized and used for subsequent reactions.
引用
收藏
页码:9647 / 9662
页数:16
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