Morgante Pierpaolo, Dughera Stefano, Ghigo Giovanni
Dipartimento di Chimica , Università di Torino Via Giuria 7 , 10125 Torino , Italy.
J Phys Chem A. 2019 Apr 4;123(13):2796-2814. doi: 10.1021/acs.jpca.9b00324. Epub 2019 Mar 22.
The generation of an iminium from amines is a way to functionalize the α carbon by coupling reactions. The reaction mechanism of the conversion of tertiary amines to iminium with CuCl(HO) as catalyst in aerobic conditions has been computationally and experimentally studied in this work. This process is initiated by the oxidation of the amine to a radical cation dichlorocuprate through the reduction of Cu to Cu. Then, the iminium dichlorocuprate is generated from the radical-ion through a hydrogen-transfer. The H atom can be accepted by molecular oxygen or by a second molecule of catalyst (in anaerobic conditions). Therefore, O also assumes the important role of acceptor along with that of regenerator of the catalyst. The experimental study confirmed the computational study and lead to the synthesis of four new molecules from the cross-coupling of N, N-diethyl- and N, N-diisoproylaniline with nitromethane and dimethylmalonate.
由胺生成亚胺鎓是通过偶联反应使α-碳官能化的一种方法。在本工作中，已通过计算和实验研究了在有氧条件下以CuCl(HO)为催化剂将叔胺转化为亚胺鎓的反应机理。该过程始于通过将Cu还原为Cu，将胺氧化为自由基阳离子二氯铜酸盐。然后，通过氢转移从自由基离子生成二氯铜酸亚胺鎓。H原子可以被分子氧或第二个催化剂分子接受（在厌氧条件下）。因此，O除了作为催化剂的再生剂外，还承担着受体的重要作用。实验研究证实了计算研究，并通过N，N-二乙基苯胺和N，N-二异丙基苯胺与硝基甲烷和丙二酸二甲酯的交叉偶联合成了四个新分子。
