Mono-N-methylation of anilines with methanol catalyzed by a manganese pincer-complex

被引:182
作者
Bruneau-Voisine, Antoine [1 ]
Wang, Ding [1 ]
Dorcet, Vincent [2 ]
Roisnel, Thierry [2 ]
Darcel, Christophe [1 ]
Sortais, Jean-Baptiste [1 ,3 ]
机构
[1] Univ Rennes 1, Inst Sci Chim Rennes, UMR CNRS 6226, Team Organometall Mat & Catalysis, 263 Ave Gen Leclerc, F-35046 Rennes, France
[2] Univ Rennes 1, Inst Sci Chim Rennes, UMR CNRS 6226, Ctr Diffractometrie X, 263 Ave Gen Leclerc, F-35046 Rennes, France
[3] Inst Univ France, 1 Rue Descartes, F-75231 Paris 05, France
关键词
Manganese; Amines; Methylation; Pincer complex; Hydrogen borrowing; CARBON-DIOXIDE; BORROWING HYDROGEN; ALPHA-ALKYLATION; AROMATIC-AMINES; STEREOSELECTIVE HYDROGENATION; REDUCTIVE METHYLATION; MECHANISTIC INSIGHTS; BOND FORMATION; C-ALKYLATION; FORMIC-ACID;
D O I
10.1016/j.jcat.2017.01.004
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The selective mono-N-methylation of anilines derivatives was achieved under mild conditions using inexpensive methanol as Cl source. Under hydrogen borrowing conditions, using a tridentate (PNP)-P-3 manganese pre-catalyst (5 mol%), a catalytic amount of base (20 mol%), for 24 h at 120 degrees C, a large variety of anilines derivatives was methylated in good to excellent yield. Mechanistic investigations allowed us to isolate and characterize by X-ray diffraction studies a de-aromatized manganese intermediate. (C) 2017 Elsevier Inc. All rights reserved.
引用
收藏
页码:57 / 62
页数:6
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