Mapping the Mechanism of Nickel-Ferrophite Catalysed Methylation of Baylis-Hillman-Derived S N 2' Electrophiles
Mapping the Mechanism of Nickel-Ferrophite Catalysed Methylation of Baylis-Hillman-Derived S N 2' Electrophiles
复制标题
绘制镍铁酸铁催化 Baylis-Hillman 衍生的 S N 2 亲电子试剂甲基化的机制
DOI：
10.1002/ejoc.200801029
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发表时间：
2009
影响因子：
2.8
通讯作者：
Novak A
中科院分区：
文献类型：
--
作者：
Novak A
用计算和实验研究了在亚铁配体存在下，Ni催化的Baylis-Hillman衍生的烯丙基亲电化合物的对映选择性甲基化反应。所获得的对映选择性的意义和程度与最初的烯丙基卤化物的离开基团和异构体结构无关。密度泛函理论研究支持选择性地形成有限数量的具有能量优势的π-烯丙基中间体。根据这些结构的能量学，可以合理地解释观察到的区域选择性和对映体选择性。(Wiley-VCH Verlag GmbH&Co.KGaA，69451温海姆，德国，2009年)
Enantioselective Ni‐catalysed methylation of Baylis–Hillman‐derived allylic electrophiles in the presence of ferrophite ligands has been investigated computationally and experimentally. The sense and degree of enantioselectivity attained is independent of both the leaving group and the isomeric structure of the initial allylic halide. DFT studies support the selective formation of a limited number of energetically favouredantiandsynπ‐allyl intermediates. The observed regio‐ and enantioselectivity can be rationalised based on the energetics of these structures. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)