Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, United States.
J Am Chem Soc. 2020 Dec 16;142(50):20930-20936. doi: 10.1021/jacs.0c09778. Epub 2020 Dec 3.
We disclose a Ni-catalyzed vicinal difunctionalization of alkenes with benzyl halides and alkylzinc reagents, which produces products with two new alkyl-alkyl bonds. This alkene dialkylation is effective in combining secondary benzyl halides and secondary alkylzinc reagents with internal alkenes, which furnishes products with three contiguous all-carbon secondary stereocenters. The products can be readily elaborated to access complex tetralene, benzosuberene, and bicyclodecene cores. The reaction also features as the most efficient alkene difunctionalization process to date with catalyst loadings down to 500 ppm and the catalytic turnover number (TON) and turnover frequency (TOF) registering up to 2 × 10 and 165 h at rt, respectively.
我们披露了一种镍催化的烯烃与苄基卤化物和烷基锌试剂的邻位双官能化反应，该反应生成了具有两个新的烷基-烷基键的产物。这种烯烃的二烷基化反应有效地结合了仲苄基卤化物和仲烷基锌试剂与内部烯烃，生成了具有三个连续全碳仲立体中心的产物。这些产物可以很容易地进行修饰，以获得复杂的四烯、苯并[ghi]苝和双环[4.4.0]癸烯核心。该反应还具有迄今为止最高效的烯烃双官能化过程，催化剂负载量低至 500ppm，催化周转数（TON）和周转频率（TOF）分别高达 2×10 和 165h（室温）。
