Aryl Bromides and Aryl Chlorides for the Direct Arylation of Benzylic Amines Mediated by Ruthenium(II)

被引:19
作者
Dastbaravardeh, Navid [1 ]
Schnuerch, Michael [1 ]
Mihovilovic, Marko D. [1 ]
机构
[1] Vienna Univ Technol, Inst Appl Synthet Chem, A-1060 Vienna, Austria
基金
奥地利科学基金会;
关键词
Homogeneous catalysis; CH activation; Cleavage reactions; Reaction mechanisms; Isotope effects; H BOND ACTIVATION; PD(OAC)(2)-CATALYZED DOMINO REACTIONS; CATALYZED DIRECT ARYLATION; C-H; OXIDATIVE ANNULATION; GRIGNARD-REAGENTS; PALLADIUM; ALKENYLATION; FUNCTIONALIZATION; ALKYLATION;
D O I
10.1002/ejoc.201300004
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The ruthenium(II)-catalyzed sp3 CH bond arylation of benzylic amines with aryl halides is reported. In the present method, aryl iodides and, more importantly, also the cheaper aryl bromides and aryl chlorides can be applied as aryl sources. Additionally, the method does not require elaborate manipulations in a glove box and can be carried out in simple screw cap vials. Potassium pivalate proved to be beneficial for the transformation with aryl bromides or iodides as aryl source, but was not required for aryl chlorides. In the latter case, the addition of PPh3 led to high conversion. 3-Methyl and 3-phenyl pyridine were established as directing groups, and the substituent in the 3-position represents a key structural feature for high conversion. The directing group can be cleaved after the transformation, which allows access to diarylmethylamines. Mechanistic studies were carried out and critically compared to mechanistic reports of related transformations.
引用
收藏
页码:2878 / 2890
页数:13
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