Department of Chemistry, University of Rochester, Rochester, New York 14627-0216, United States.
Org Lett. 2012 Mar 16;14(6):1476-9. doi: 10.1021/ol300217x. Epub 2012 Feb 23.
Unsymmetrical dialkyl ketones can be directly prepared by the nickel-catalyzed reductive coupling of carboxylic acid chlorides or (2-pyridyl)thioesters with alkyl iodides or benzylic chlorides. A wide variety of functional groups are tolerated by this process, including common nitrogen protecting groups and C-B bonds. Even hindered ketones flanked by tertiary and secondary centers can be formed. The mechanism is proposed to involve the reaction of a (L)Ni(alkyl)(2) intermediate with the carboxylic acid derivative.
不对称二烷基酮可以通过镍催化的羧酸氯或（2-吡啶基）硫酯与碘代烷或苄基氯的还原偶联直接制备。该过程可以容忍多种官能团，包括常见的氮保护基团和 C-B 键。甚至受位阻影响的酮，其两侧为叔碳和仲碳中心，也可以形成。该反应机制被认为涉及 (L)Ni(烷基)(2) 中间体与羧酸衍生物的反应。
