Li Zi-Qi, Apolinar Omar, Deng Ruohan, Engle Keary M
Department of Chemistry, The Scripps Research Institute 10550 North Torrey Pines Road La Jolla California 92037 USA
Chem Sci. 2021 Jul 13;12(33):11038-11044. doi: 10.1039/d1sc03121j. eCollection 2021 Aug 25.
We report a full account of our research on nickel-catalyzed Markovnikov-selective hydroarylation and hydroalkenylation of non-conjugated alkenes, which has yielded a toolkit of methods that proceed under mild conditions with alkenyl sulfonamide, ketone, and amide substrates. Regioselectivity is controlled through catalyst coordination to the native Lewis basic functional groups contained within these substrates. To maximize product yield, reaction conditions were fine-tuned for each substrate class, reflecting the different coordination properties of the directing functionality. Detailed kinetic and computational studies shed light on the mechanism of this family of transformations, pointing to transmetalation as the turnover-limiting step.
我们全面报告了我们关于镍催化非共轭烯烃的马氏选择性氢芳基化和氢烯基化的研究，该研究产生了一套方法，可在温和条件下与烯基磺酰胺、酮和酰胺底物进行反应。区域选择性是通过催化剂与这些底物中所含的天然路易斯碱性官能团配位来控制的。为了使产物收率最大化，针对每种底物类别对反应条件进行了微调，这反映了导向官能团不同的配位性质。详细的动力学和计算研究揭示了这一系列转化反应的机理，表明金属转移是周转限制步骤。
