Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
J Am Chem Soc. 2013 Jan 30;135(4):1585-92. doi: 10.1021/ja3116718. Epub 2013 Jan 14.
The synthesis and characterization of the air-stable nickel(II) complex trans-(PCy(2)Ph)(2)Ni(o-tolyl)Cl is described in conjunction with an investigation of its use for the Mizoroki-Heck-type, room temperature, internally selective coupling of substituted benzyl chlorides with terminal alkenes. This reaction, which employs a terminal alkene as an alkenylmetal equivalent, provides rapid, convergent access to substituted allylbenzene derivatives in high yield and with regioselectivity greater than 95:5 in nearly all cases. The reaction is operationally simple, can be carried out on the benchtop with no purification or degassing of solvents or reagents, and requires no exclusion of air or water during setup. Synthesis of the precatalyst is accomplished through a straightforward procedure that employs inexpensive, commercially available reagents, requires no purification steps, and proceeds in high yield.
描述了空气稳定的镍（II）配合物反式-（PCy（2）Ph）（2）Ni（o-甲苯基）Cl 的合成和表征，并研究了其在室温下 Mizoroki-Heck 型、内部选择性取代苄基氯化物与末端烯烃偶联中的应用。该反应采用末端烯烃作为烯基金属等价物，提供了快速、收敛的方法，以高产率和大于 95:5 的区域选择性得到取代的烯丙基苯衍生物，几乎在所有情况下都是如此。该反应操作简单，可在台面上进行，无需对溶剂或试剂进行纯化或脱气，在设置过程中也无需排除空气或水。前催化剂的合成通过一种简单的方法完成，该方法使用廉价的商业上可获得的试剂，不需要纯化步骤，并且产率很高。
