Ruthenium-Catalyzed Hydrogenation of Nitriles: Insights into the Mechanism

被引:152
作者
Reguillo, Rebeca [1 ]
Grellier, Mary [1 ]
Vautravers, Nicolas [1 ]
Vendier, Laure [1 ]
Sabo-Etienne, Sylviane [1 ]
机构
[1] Univ Toulouse, Chim Coordinat Lab, CNRS, UPS,INPT, F-31077 Toulouse, France
关键词
PRIMARY AMINES; COMPLEXES; LIGANDS; IMINE; DEHYDROGENATION; BENZONITRILE; REACTIVITY; ACTIVATION; REDUCTION; HYDRIDE;
D O I
10.1021/ja102759z
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Hydrogenation of benzonitrile into benzylannine is catalyzed under very mild conditions by the ruthenium bis(dihydrogen) complex RuH2(H-2)(2)(PCyp(3))(2), incorporating two tricyclopentylphosphines. Two key intermediates have been isolated, resulting from the activation of benzonitrile at early stages of activation, i.e., either N-coordination through the nitrite function or first hydrogenation with benzylimine formation, followed by, thanks to C-H activation, coordination at ruthenium as an orthometalated ligand.
引用
收藏
页码:7854 / +
页数:3
相关论文
共 19 条
[1]   Ruthenium N-heterocyclic carbene catalysts for selective reduction of nitriles to primary amines [J].
Addis, Daniele ;
Enthaler, Stephan ;
Junge, Kathrin ;
Wendt, Bianca ;
Beller, Matthias .
TETRAHEDRON LETTERS, 2009, 50 (26) :3654-3656
[2]   Bis σ-Bond Dihydrogen and Borane Ruthenium Complexes: Bonding Nature, Catalytic Applications, and Reversible Hydrogen Release [J].
Alcaraz, Gilles ;
Grellier, Mary ;
Sabo-Etienne, Sylviane .
ACCOUNTS OF CHEMICAL RESEARCH, 2009, 42 (10) :1640-1649
[3]   MONOMERIC AND DIMERIC RUTHENIUM(II) ETA-2-DIHYDROGEN COMPLEXES WITH TRICYCLOHEXYLPHOSPHINE COLIGANDS [J].
ARLIGUIE, T ;
CHAUDRET, B ;
MORRIS, RH ;
SELLA, A .
INORGANIC CHEMISTRY, 1988, 27 (04) :598-599
[4]   Synthesis and characterization of OsX{NH=C(Ph)C6H4}H2(PiPr3)2 (X = H, Cl, Br, I):: Nature of the H2 unit and its behavior in solution [J].
Barea, G ;
Esteruelas, MA ;
Lledos, A ;
Lopez, AM ;
Onate, E ;
Tolosa, JI .
ORGANOMETALLICS, 1998, 17 (18) :4065-4076
[5]  
Beatty R. P., 1996, WO Patent, Patent No. [96/23802-804, 9623802804]
[6]   Versatile reactivity of the bis(dihydrogen) complex RuH2(H-2)(2)(PCy(3))(2) toward functionalized olefins: Olefin coordination versus hydrogen transfer via the stepwise dehydrogenation of the phosphine ligand [J].
Borowski, AF ;
SaboEtienne, S ;
Christ, ML ;
Donnadieu, B ;
Chaudret, B .
ORGANOMETALLICS, 1996, 15 (05) :1427-1434
[7]   Displacement of phenyl and styryl ligands by benzophenone imine and 2-vinylpyridine on ruthenium and osmium [J].
Buil, Maria L. ;
Esteruelas, Miguel A. ;
Goni, Eva ;
Olivan, Montserrat ;
Onate, Enrique .
ORGANOMETALLICS, 2006, 25 (12) :3076-3083
[8]   Cleavage of H-C(sp2) and C(sp2)-X bonds (X = alkyl, aryl, OR, NR2):: Facile decarbonylation, isonitrile abstraction, or dehydrogenation of aldehydes, esters, amides, amines, and imines by [RuHCl(PiPr3)2]2 [J].
Coalter, JN ;
Huffman, JC ;
Caulton, KG .
ORGANOMETALLICS, 2000, 19 (18) :3569-3578
[9]   A General and Environmentally Benign Catalytic Reduction of Nitriles to Primary Amines [J].
Enthaler, Stephan ;
Addis, Daniele ;
Junge, Kathrin ;
Erre, Giulia ;
Beller, Matthias .
CHEMISTRY-A EUROPEAN JOURNAL, 2008, 14 (31) :9491-9494
[10]   A Practical and Benign Synthesis of Primary Amines through Ruthenium-Catalyzed Reduction of Nitriles [J].
Enthaler, Stephan ;
Junge, Kathrin ;
Addis, Daniele ;
Erre, Giulia ;
Beller, Matthias .
CHEMSUSCHEM, 2008, 1 (12) :1006-1010