Department of Chemistry, McGill University, 801 Sherbrooke Street West, Montreal, QC H3A 2K6, Canada.
Chemistry. 2010 Jul 19;16(27):8162-6. doi: 10.1002/chem.201000240.
The ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate [BMIm][BF(4)] has demonstrated high efficiency when applied as a solvent in the oxidative nitro-Mannich carbon--carbon bond formation. The copper-catalyzed cross-dehydrogenative coupling (CDC) between N-phenyltetrahydroisoquinoline and nitromethane in [BMIm][BF(4)] occurred with high yield under the described reaction conditions. Both the ionic liquid and copper catalyst were recycled nine times with almost no lost of activity. The electrochemical behavior of the tertiary amine substrate and beta-nitroamine product was investigated employing [BMIm][BF(4)] as electrolyte solvent. The potentiostatic electrolysis in ionic liquid afforded the desired product with a high yield. This result and the cyclic voltammetric investigation provide a better understanding of the reaction mechanism, which involves radical and iminium cation intermediates.
离子液体 1-丁基-3-甲基咪唑四氟硼酸盐 [BMIm][BF(4)] 在作为溶剂应用于氧化硝基-Mannich 碳-碳键形成时表现出高效率。在描述的反应条件下，N-苯基四氢异喹啉和硝基甲烷在 [BMIm][BF(4)] 中的铜催化交叉脱氢偶联 (CDC) 以高产率发生。离子液体和铜催化剂在几乎没有失去活性的情况下循环使用了九次。使用 [BMIm][BF(4)] 作为电解质溶剂，研究了叔胺底物和β-硝基胺产物的电化学行为。在离子液体中的恒电位电解以高产率得到了所需的产物。这一结果和循环伏安法研究提供了对反应机理的更好理解，该机理涉及自由基和亚胺阳离子中间体。
