4458-31-5Relevant academic research and scientific papers
Catalytic reduction of amides to amines by electrophilic phosphonium cations via FLP hydrosilylation
Augurusa, Alessandra,Mehta, Meera,Perez, Manuel,Zhu, Jiangtao,Stephan, Douglas W.
supporting information, p. 12195 - 12198 (2016/10/21)
A catalytic methodology for the conversion of amides to amines is reported. Of the 25 examples described, 14 examples involve the reduction of N-trifluoroacetamides to the corresponding trifluoroethylamines. These reductions are achieved by catalytic hydrosilylation of the amide mediated by an electrophilic phosphonium cation (EPC) catalyst.
Modular Attachment of Appended Boron Lewis Acids to a Ruthenium Pincer Catalyst: Metal-Ligand Cooperativity Enables Selective Alkyne Hydrogenation
Tseng, Kuei-Nin T.,Kampf, Jeff W.,Szymczak, Nathaniel K.
supporting information, p. 10378 - 10381 (2016/09/04)
A new series of bifunctional Ru complexes with pendent Lewis acidic boranes were prepared by late-stage modification of an active hydrogen-transfer catalyst. The appended boranes modulate the reactivity of a metal hydride as well as catalytic hydrogenations. After installing acidic auxiliary groups, the complexes become multifunctional and catalyze the cis-selective hydrogenation of alkynes with higher rates, conversions, and selectivities compared with the unmodified catalyst.
Catalytic hydrogenation of amides to amines under mild conditions
Stein, Mario,Breit, Bernhard
supporting information, p. 2231 - 2234 (2013/03/28)
Under (not so much) pressure: A general method for the hydrogenation of tertiary and secondary amides to amines with excellent selectivity using a bimetallic Pd-Re catalyst has been developed. The reaction proceeds under low pressure and comparatively low temperature. This method provides organic chemists with a simple and reliable tool for the synthesis of amines. Copyright
Continuous gas-phase hydroaminomethylation using supported ionic liquid phase catalysts
Schneider, Martin Johannes,Lijewski, Martin,Woelfel, Rene,Haumann, Marco,Wasserscheid, Peter
, p. 6996 - 6999 (2013/07/26)
Just SILP-ing through: Hydroaminomethylation of ethylene and diethylamine to diethylpropylamine is demonstrated as a continuous gas-phase reaction (see picture) using a supported ionic liquid phase (SILP) to immobilize the applied homogenous Rh-Xantphos catalyst. Highly selective and long-term stable (18 days) catalyst operation was obtained if the ionic liquid was of low basicity and lipophilicity combined with a porous activated carbon support. Copyright
Selective hydrogenation of amides using ruthenium/ molybdenum catalysts
Beamson, Graham,Papworth, Adam J.,Philipps, Charles,Smith, Andrew M.,Whyman, Robin
experimental part, p. 869 - 883 (2010/07/05)
Recyclable, heterogeneous bimetallic ruthenium/molybdenum catalysts, formed in situ from triruthenium dodecacarbonyl [Ru3(CO)12] and molybdenum hexacarbonyl [Mo(CO)6], are effective for the selective liquid phase hydrogenation of cyclohexylcarboxamide (CyCONH2) to cyclohexanemethylamine (CyCH2NH2), with no secondary or tertiary amine by-product formation. Variation of Mo:Ru composition reveals both synergistic and poisoning effects, with the optimum combination of conversion and selectivity at ca. 0.5, and total inhibition of catalysis evident at ≥1. Good amide conversions are noted within the reaction condition regimes 20100 bar hydrogen and 145-160°C. The order of reactivity of these catalysts towards reduction of different amide functional groups is primary > tertiary ? secondary. In situ HP-FT-IR spectroscopy confirms that catalyst genesis occurs during an induction period associated with decomposition of the organometallic precursors. Ex situ characterisation, using XRD, XPS and EDX-STEM, for active Mo:Ru compositions, has provided evidence for intimately mixed ca. 2.5-4 nm particles that contain metallic ruthenium, and molybdenum (in several oxidation states, including zero).
Hydrogenation of amides by the use of bimetallic catalysts consisting of group 8 to 10, and group 6 or 7 metals
Hirosawa, Chitaru,Wakasa, Noriko,Fuchikami, Takamasa
, p. 6749 - 6752 (2007/10/03)
Hydrogenation of amides can be catalyzed by bimetallic systems, which consist of Group 8 to 10 late transition-metals and Group 6 or 7 early transition-metals, under the mild conditions to afford the corresponding amines selectively in good to excellent yields.
Transalkylation Reaction. Homogeneous Catalytic Formation of C-N Bonds
Wilson, Robert B.,Laine, Richard M.
, p. 361 - 369 (2007/10/02)
We have performed kinetic and mechanistic studies on homogeneous ruthenium-catalyzed transalkylation of tertiary amines.From these studies we have derived a kinetic expression for transalkylation catalysis based on initial reaction rates.We find that transalkylation proceeds most efficiently in alcoholic solvents (e.g., MeOH or EtOH), under a slight pressure of CO, with a mixed-metal, iron-ruthenium catalyst.The mechanism appears to be in one which a metal cluster of at least two and most probably three atoms binds the amine through insertion into an α C-H bond to give a metallazacyclopropane or metal-iminium complex.Nucleophilic attack by free amine on the complex, or an immediate derivative, follows, and subsequent rearrangement of the intermediate formed gives transalkylation products.The catalyst system has been tested as a synthetic tool for the oligomerization and cyclization of tertiary diamines.These preliminary studies have been quite succesful.Thus, N,N,N',N'-tetramethylethylenediamine can be transformed into Me3N and N,N'-dimethylpiperazine with good conversion and high selectivity.N,N,N',N'-Tetraethylethylenediamine can be transformed into Et3N and the linear, perethyl, ethylenediamine dimer, trimer, tetramer, and pentamer with excellent conversion.
Homogeneous Catalytic Activation of C-N Bonds. Alkyl Exchange between Tertiary amines.
Shvo, Youval,Laine, Richard M.
, p. 753 - 754 (2007/10/02)
We have found that several transition metal cluster compounds act as homogeneous catalyst precursors in alkyl exchange reactions of tertiary amines; treatment of mixtures of Et3N and Pr3N with either Ru3(CO)12, Os3(CO)12, or Ir4(CO)12 and water leads to very efficient alkyl exchange.
