Falciola Caroline A, Alexakis Alexandre
Département de Chimie Organique, Université de Genève, Quai E-Ansermet 30, 1211 Genève 4, Switzerland.
Chemistry. 2008;14(34):10615-27. doi: 10.1002/chem.200801309.
Enantioselective allylic alkylation with an organomagnesium reagent catalyzed by copper thiophene carboxylate (CuTC) was carried out on difunctionalized substrates, such as commercially available 1,4-dichloro-2-butene and 1,4-dibromo-2-butene, and on similar compounds of higher substitution pattern of the olefin for the formation of all-carbon chiral quaternary centers. The high regioselectivity obtained throughout the reactions favored good regiocontrol for the addition of phenyl Grignard reagents. Other difunctionalized substrates (allylic ethers and allylic alcohols) also underwent asymmetric S(N)2' substitution.
在二官能化底物（如市售的1,4 - 二氯 - 2 - 丁烯和1,4 - 二溴 - 2 - 丁烯）以及具有更高烯烃取代模式的类似化合物上，进行了由噻吩羧酸铜（CuTC）催化的与有机镁试剂的对映选择性烯丙基烷基化反应，以形成全碳手性季碳中心。整个反应过程中获得的高区域选择性有利于苯基格氏试剂加成的良好区域控制。其他二官能化底物（烯丙基醚和烯丙醇）也经历了不对称S(N)2'取代反应。
