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
相关论文
共 110 条
[1]   Recent development in catalytic technologies for methanol synthesis from renewable sources: A critical review [J].
Ali, Khozema Ahmed ;
Abdullah, Ahmad Zuhairi ;
Mohamed, Abdul Rahman .
RENEWABLE & SUSTAINABLE ENERGY REVIEWS, 2015, 44 :508-518
[2]  
Anastas P., 1998, GREEN CHEM THEORY PR
[3]  
[Anonymous], CATALYSIS PRECIOUS M
[4]   The Catalytic Amination of Alcohols [J].
Baehn, Sebastian ;
Imm, Sebastian ;
Neubert, Lorenz ;
Zhang, Min ;
Neumann, Helfried ;
Beller, Matthias .
CHEMCATCHEM, 2011, 3 (12) :1853-1864
[5]   Iron Catalysis in Organic Synthesis [J].
Bauer, Ingmar ;
Knoelker, Hans-Joachim .
CHEMICAL REVIEWS, 2015, 115 (09) :3170-3387
[6]   Achiral and chiral transition metal complexes with modularly designed tridentate PNP pincer-type ligands based on N-heterocyclic diamines [J].
Benito-Garagorri, D ;
Becker, E ;
Wiedermann, J ;
Lackner, W ;
Pollak, M ;
Mereiter, K ;
Kisala, J ;
Kirchner, K .
ORGANOMETALLICS, 2006, 25 (08) :1900-1913
[7]   Modularly designed transition metal PNP and PCP pincer complexes based on aminophosphines: Synthesis and catalytic applications [J].
Benito-Garagorri, David ;
Kirchner, Karl .
ACCOUNTS OF CHEMICAL RESEARCH, 2008, 41 (02) :201-213
[8]   Ruthenium-Catalyzed Reductive Methylation of Imines Using Carbon Dioxide and Molecular Hydrogen [J].
Beydoun, Kassem ;
Ghattas, Ghazi ;
Thenert, Katharina ;
Klankermayer, Juergen ;
Leitner, Walter .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2014, 53 (41) :11010-11014
[9]   Ruthenium-Catalyzed Direct Methylation of Primary and Secondary Aromatic Amines Using Carbon Dioxide and Molecular Hydrogen [J].
Beydoun, Kassem ;
vom Stein, Thorsten ;
Klankermayer, Juergen ;
Leitner, Walter .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2013, 52 (36) :9554-9557
[10]   Carbon Dioxide Reduction to Methylamines under Metal-Free Conditions [J].
Blondiaux, Enguerrand ;
Pouessel, Jacky ;
Cantat, Thibault .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2014, 53 (45) :12186-12190