Intermolecular Redox-Neutral Amine C-H Functionalization Induced by the Strong Boron Lewis Acid B(C6F5)3 in the Frustrated Lewis Pair Regime
Intermolecular Redox-Neutral Amine C-H Functionalization Induced by the Strong Boron Lewis Acid B(C6F5)3 in the Frustrated Lewis Pair Regime
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DOI：
10.1002/chem.201700477
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发表时间：
2017-04-03
影响因子：
4.3
通讯作者：
Erker, Gerhard
中科院分区：
文献类型：
--
作者：
Chen, Guo-Qiang;Kehr, Gerald;Erker, Gerhard
N，N-二甲基甲三胺经二甲基乙炔二羧酸酯和强硼Lewis酸B（C6F5）处理后，发生分子间氧化还原-中性C-H活化/C-C偶联过程(3)。同样，N，N-二甲基甲三胺与两个摩尔当量的丙烯酸乙酯反应，得到各自的不饱和偶联产物，H-2转移到丙烯酸酯上，形成丙酸乙酯/B(C6F5)(3)加合物。N，N-二甲基甲三胺在皮尔斯硼烷处理后，在苯基邻位sp(3)-碳原子上也发生C-H活化，形成二氢[HB(C6F5)(2)]。用DFT计算分析了N，N-二甲基甲三胺的后两个反应。
N,N-Dimethylmesitylamine undergoes an intermolecular redox-neutral C-H activation/C-C coupling process upon treatment with dimethyl acetylenedicarboxylate and the strong boron Lewis acid B(C6F5)(3). Similarly, N,N-dimethylmesitylamine reacts with two molar equivalents of ethyl acrylate to give the respective unsaturated coupling product with H-2 transfer to the acrylic ester to form the ethyl propionate/B(C6F5)(3) adduct. N,N-Dimethylmesitylamine also undergoes a C-H activation at the benzylic ortho sp(3)-carbon atom with dihydrogen formation upon treatment with Piers' borane [HB(C6F5)(2)]. The last two reactions of N,N-dimethylmesitylamine were analyzed by DFT calculations.