102-05-6Relevant articles and documents
Enhancing the Catalytic Properties of Ruthenium Nanoparticle-SILP Catalysts by Dilution with Iron
Luska, Kylie L.,Bordet, Alexis,Tricard, Simon,Sinev, Ilya,Grünert, Wolfgang,Chaudret, Bruno,Leitner, Walter
, p. 3719 - 3726 (2016)
The partial replacement of ruthenium by iron ("dilution") provided enhanced catalytic activities and selectivities for bimetallic iron-ruthenium nanoparticles immobilized on a supported ionic liquid phase (FeRuNPs@SILP). An organometallic synthetic approach to the preparation of FeRuNPs@SILP allowed for a controlled and flexible incorporation of Fe into bimetallic FeRu NPs. The hydrogenation of substituted aromatic substrates using bimetallic FeRuNPs@SILP showed high catalytic activities and selectivities for the reduction of a variety of unsaturated moieties without saturation of the aromatic ring. The formation of a bimetallic phase not only leads to an enhanced differentiation of the hydrogenation selectivity, but even reversed the order of functional group hydrogenation in certain cases. In particular, bimetallic FeRuNPs@SILP (Fe:Ru = 25:75) were found to exhibit accelerated reaction rates for C=O hydrogenation within furan-based substrates which were >4 times faster than monometallic RuNPs@SILP. Thus, the controlled incorporation of the non-noble metal into the bimetallic phase provided novel catalytic properties that could not be obtained using either of the monometallic catalysts.
Fe@Pd/C: An efficient magnetically separable catalyst for direct reductive amination of carbonyl compounds using environment friendly molecular hydrogen in aqueous reaction medium
Patil, Nilesh M.,Bhanage, Bhalchandra M.
, p. 182 - 189 (2015)
Direct reductive amination of carbonyl compounds with variety of amines has been reported by using magnetically separable Fe@Pd/C as an efficient catalyst in aqueous reaction medium. The developed methodology offers synthesis of various secondary and tertiary amines using different aldehydes and ketones with amines giving excellent yield. Moreover, the magnetically separable Fe@Pd/C catalyst was easily separated from reaction mixture and can be recycled for further reaction.
Bifunctional (cyclopentadienone)iron-tricarbonyl complexes: Synthesis, computational studies and application in reductive amination
Moulin, Solenne,Dentel, Helene,Pagnoux-Ozherelyeva, Anastassiya,Gaillard, Sylvain,Poater, Albert,Cavallo, Luigi,Lohier, Jean-Francois,Renaud, Jean-Luc
, p. 17881 - 17890 (2013)
Reductive amination under hydrogen pressure is a valuable process in organic chemistry to access amine derivatives from aldehydes or ketones. Knoelker's complex has been shown to be an efficient iron catalyst in this reaction. To determine the influence of the substituents on the cyclopentadienone ancillary ligand, a series of modified Knoelker's complexes was synthesised and fully characterised. These complexes were also transformed into their analogous acetonitrile iron-dicarbonyl complexes. Catalytic activities of these complexes were evaluated and compared in a model reaction. The scope of this reaction is also reported. For mechanistic insights, deuterium-labelling experiments and DFT calculations were undertaken and are also presented. Festival of amination: Two series of modified Knoelker's complexes were synthesised and applied in the reductive amination of various carbonyl derivatives with primary or secondary amines (see scheme, TIPS = triisopropylsilyl). For a mechanistic insight, deuterium-labelling experiments and DFT calculations were undertaken and are also presented. Copyright
THE HOMOGENEOUSLY CATALYSED SYNTHESIS OF N-METHYLDIALKYLAMINES FROM N-METHYL AND N,N-DIMETHYLALKYLAMIMES
Arcelli, Antonio,Bui-The-Khai,Porzi, Gianni
, p. C31 - C34 (1982)
N-Methyl and N,N-dimethylalkylamines are converted into N-methyldialkylamines in good yields when heated at 180 deg C in the presence of a catalytic amount of RuCl2(Ph3P)3.
Synthesis of Amines via Carbon-Sulfur Bond Cleavages of Substituted Aminomethyl Sulfides with Organolithium Reagents: Aminocarbene Route to Enamines and Sterically Hindered Amines
Eisch, John J.,McNulty, John F.,Shi, Xian
, p. 7 - 9 (1994)
N-Substituted and N,N-disubstituted aminomethyl sulfides can be converted into secondary and tertiary amines, respectively, by organolithium reagents in high yields, regardless of whether the N-substituent is alkyl or aryl; for the former case, imines, and for the latter case, aminocarbenes, are the most likely intermediates.
Cobalt carbonyl-based catalyst for hydrosilylation of carboxamides
Dombray, Thomas,Helleu, Camille,Darcel, Christophe,Sortais, Jean-Baptiste
, p. 3358 - 3362 (2013)
The cobalt carbonyl [Co2(CO)8] complex is employed as a useful catalyst for the reduction of tertiary amides to the corresponding tertiary amines using 1,1,3,3-tetramethyldisiloxane (TMDS) and poly(methylhydrosiloxane) (PMHS) as silane reagents under thermal (100 °C) or photo-assisted conditions (UV, 350 nm at room temperature). Of particular interest, a low catalytic amount (0.5 mol%) of [Co2(CO)8] is used to perform the reaction with 2.2 equiv. of PMHS at 100 °C for 3 h. This reaction is the first example of a cobalt-catalyzed hydrosilylation of amides. Copyright
Fluorocarbon accelerated supported transformations (FAST) on REM resin
Morphy,Rankovic, Zoran,York, Mark
, p. 7509 - 7511 (2001)
The use of perfluorous organic solvents in the solid-phase synthesis of 3° amines on REM resin allows a large reduction in both reaction time and the amount of amine required for a successful Michael reaction. Yields of products were typically at least three fold greater than those observed with standard solvents under the same conditions.
Borohydride reductions in dichloromethane: A convenient, environmentally compatible procedure for the methylation of amines
Bhattacharyya
, p. 2061 - 2069 (1995)
The combination of zinc chloride and sodium borohydride in dichloromethane is used to effect reductive aminations of formaldehyde with a variety of primary and secondary amines containing potentially acid-sensitive functional groups in good to excellent yields.
Reductive methylation of primary and secondary amines and amino acids by aqueous formaldehyde and zinc
da Silva, Renato A.,Estevam, Idália H.S.,Bieber, Lothar W.
, p. 7680 - 7682 (2007)
Amines can be methylated when treated with formaldehyde and zinc in aqueous medium. Selective mono- or dimethylation can be achieved by proper choice of pH, stoichiometry and reaction time. This method can also be applied for amino acids.
A new method for generation of non-stabilized α-amino-substituted carbanions by the reaction of magnesium carbenoids with N-lithio arylamines: their reactivity and a new synthesis of α-amino acid derivatives
Satoh, Tsuyoshi,Osawa, Atsushi,Ohbayashi, Tohru,Kondo, Atsushi
, p. 7892 - 7901 (2006)
Magnesium carbenoids were generated from aryl 1-chloroalkyl sulfoxides with i-PrMgCl in THF at low temperature in quantitative yields. The magnesium carbenoids were found to be reactive with N-lithio alkylamines to afford an olefin, which was derived from dimerization of the magnesium carbenoid, in moderate yield. On the other hand, reaction of the magnesium carbenoids with N-substituted N-lithio arylamines gave non-stabilized α-amino-substituted carbanions in good yields. Reactivity of the α-amino-substituted carbanions with some electrophiles was investigated and it was found that ethyl chloroformate reacted to give α-amino acid derivatives in good yields. As a whole, a new method for one-pot, three-component combined synthesis of α-amino acid derivatives from aryl 1-chloroalkyl sulfoxides was realized.
