Vuagnoux-d'Augustin Magali, Alexakis Alexandre
Département de Chimie Organique, Université de Genève, 30, quai Ernest Ansermet, 1211 Geneve, Switzerland.
Chemistry. 2007;13(34):9647-62. doi: 10.1002/chem.200701001.
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]2C6H6) 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. Then, the generated enantioenriched aluminium enolates and the chiral conjugate adducts were functionalized and used for subsequent reactions.
在催化量的铜盐（噻吩羧酸铜、[Cu(CH₃CN)₄]BF₄或[CuOTf]₂C₆H₆）和基于三齿磷酰胺配体存在下，三甲基铝、三乙基铝和乙烯基铝物种对多种2-或3-取代的烯酮（环戊-2-烯酮、环己-2-烯酮、3-甲基环庚-2-烯酮）进行对映选择性共轭加成。因此，可以构建手性季碳中心，在对实验条件进行严格优化后，对映体过量率高达98%。结果表明，主要的重要参数是试剂引入的顺序。然后，将生成的对映体富集的烯醇铝盐和手性共轭加合物进行官能化，并用于后续反应。
