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Angew.Chem.Int.Ed.2016,55,2186~2190轴手性化合物因其具有独特的不可旋转的手性轴,在不对称催化等方面中有非常重要的应用.构建轴手性化合物最直接的方法之一是过渡金属催化的多组分的交叉偶联.中国科学技术大学顾振华课题组通过钯催化的溴代芳烃与腙化合物的偶联反应,以优异的产率得到了高对映选择性(ee约97%)的烯基芳烃轴手性化合物.反应通过芳基钯物种与卡宾形成钯卡宾中间体,最后迁移插入得到季碳钯物种,β-氢消除得到产物同时控制手性的产生.反应产率高,底物适用性好.产物可方便地转化为烯基膦配体(99%ee),并成功应用于不对称的烯丙基取代反应.
Angew.Chem.Int.Ed.2016,55,2186 ~ 2190 Axis-chiral compounds have very important applications in the field of asymmetric catalysis because of their unique non-rotatable chiral axes. One of the direct methods is the transition metal-catalyzed cross-coupling of multicomponent materials.University of Science and Technology of China Gu Zhenhua’s group obtained high-enantiopure results with excellent yields via palladium-catalyzed coupling reactions of brominated aromatics with hydrazone compounds Selectivity (ee about 97%) of the alkenyl aromatic hydrocarbon axis of the chiral compounds. The reaction through aryl palladium species and carbene formation of palladium carbene intermediates, and finally migrate to obtain quaternary palladium species, β-hydrogen elimination of the product while controlling the chiral The yield of the reaction is high and the substrate has good applicability.The product can be easily converted into the alkenylphosphine ligand (99% ee) and successfully applied in the asymmetric allyl substitution reaction.