103-49-1Relevant articles and documents
Reductive amination of aldehydes and ketones with 2-(Tributylamino)- ethoxyborohydride
Mohanazadeh, Farajollah,Forozani, Mehdi,Taheri, Azam
, p. 1187 - 1189 (2007)
A new ionic liquid is presented as a medium and reducing agent for the reductive amination of aldehydes and ketones.
Integrated Electro-Biocatalysis for Amine Alkylation with Alcohols
Pe?afiel, Itziar,Dryfe, Robert A. W.,Turner, Nicholas J.,Greaney, Michael F.
, p. 864 - 867 (2021)
The integration of electro and bio-catalysis offers new ways of making molecules under very mild, environmentally benign conditions. We show that TEMPO mediated electro-catalytic oxidation of alcohols can be adapted to work in aqueous buffers, with minimal organic co-solvent, enabling integration with biocatalytic reductive amination using the AdRedAm enzyme. The combined process offers a new approach to amine alkylation with native alcohols, a key bond formation in the chemical economy that is currently achieved via precious metal-catalyzed hydrogen-borrowing technologies. The electrobio transformation is effective for primary and secondary alcohols undergoing coupling with allyl, propargyl, benzyl, and cyclopropyl amines, and has been adapted for use with solid-supported AdRedAm for ease of operation.
A general approach to mono- and bimetallic organometallic nanoparticles
Mavila, Sudheendran,Rozenberg, Illya,Lemcoff, N. Gabriel
, p. 4196 - 4203 (2014)
A comprehensive methodology to prepare nanometric size organometallic particles (ONPs) containing rhodium(i), iridium(i) and nickel(0) with ROMP-derived polycycloocta-1,5-diene (pCOD) by a controlled single chain collapse mechanism was developed. The polymeric complexes could be produced via direct exchange of the respective labile ligands of metal complexes by the 1,5-hexadiene elements in pCOD, or via in situ reduction of metal ions in the presence of the polymer. These well-defined π-bound polymeric complexes were characterized by UV-Vis spectroscopy, dynamic light scattering (DLS) and size exclusion chromatography (SEC) measurements and the resulting polymer sizes were found to be inversely proportional to the amount of metal added due to concomitant single chain collapse. Moreover, these procedures were readily extended to the synthesis of organobimetallic nanoparticles containing two metals; which could be added in commutative order and specific metal ratios. The embedded metal elements were found to be readily accessible for applications in catalysis, where the close proximity of the catalytic centers led to distinctive reactivity compared to the isolated complexes.
One-pot reductive amination of aldehydes and ketones with α-picoline-borane in methanol, in water, and in neat conditions
Sato, Shinya,Sakamoto, Takeshi,Miyazawa, Etsuko,Kikugawa, Yasuo
, p. 7899 - 7906 (2004)
A one-pot reductive amination of aldehydes and ketones with amines using α-picoline-borane as a reducing agent is described. The reaction has been carried out in MeOH, in H2O, and in neat conditions in the presence of small amounts of AcOH. This is a highly efficient and mild procedure that is applicable for a wide variety of substrates. In particular, this is the first successful demonstration that this type of reaction can be carried out in water and in neat conditions.
A new method for deprotection of benzothiazolesulfonamides using a thiol and base
Wuts, Peter G. M.,Gu, Rui Lin,Northuis, Jill M.,Thomas, Collette L.
, p. 9155 - 9156 (1998)
Benzothiazolesulfonamides of primary and secondary amines are efficiently cleaved by a nucleophilic aromatic substitution with a thiol and a base such as potassium t-butoxide or diisopropylethyl amine in DMF.
Highly economical and direct amination of sp3carbon using low-cost nickel pincer catalyst
Brandt, Andrew,Rangumagar, Ambar B.,Szwedo, Peter,Wayland, Hunter A.,Parnell, Charlette M.,Munshi, Pradip,Ghosh, Anindya
, p. 1862 - 1874 (2021)
Developing more efficient routes to achieve C-N bond coupling is of great importance to industries ranging from products in pharmaceuticals and fertilizers to biomedical technologies and next-generation electroactive materials. Over the past decade, improvements in catalyst design have moved synthesis away from expensive metals to newer inexpensive C-N cross-coupling approaches via direct amine alkylation. For the first time, we report the use of an amide-based nickel pincer catalyst (1) for direct alkylation of amines via activation of sp3 C-H bonds. The reaction was accomplished using a 0.2 mol% catalyst and no additional activating agents other than the base. Upon optimization, it was determined that the ideal reaction conditions involved solvent dimethyl sulfoxide at 110 °C for 3 h. The catalyst demonstrated excellent reactivity in the formation of various imines, intramolecularly cyclized amines, and substituted amines with a turnover number (TON) as high as 183. Depending on the base used for the reaction and the starting amines, the catalyst demonstrated high selectivity towards the product formation. The exploration into the mechanism and kinetics of the reaction pathway suggested the C-H activation as the rate-limiting step, with the reaction second-order overall, holding first-order behavior towards the catalyst and toluene substrate.
Graphene-supported NiPd alloy nanoparticles: A novel and highly efficient heterogeneous catalyst system for the reductive amination of aldehydes
Ni?anci, Bilal,Ganjehyan, Khadijeh,Metin, ?nder,Da?tan, Arif,T?r?k, Béla
, p. 191 - 197 (2015)
A novel and highly efficient heterogeneous catalytic reductive amination of aldehydes is described. The recently developed graphene supported NiPd alloy nanoparticle (G-NiPd) catalyst using ammonia borane (AB) as a green, stable and safe hydrogen donor was used in a water/methanol mixture (v/v = 2/3) under ambient conditions. The catalytic system was successfully applied in the reductive amination of various substituted aldehydes with amines and the corresponding products were obtained in (up to) 99% yield in 6 h. The G-NiPd catalyst could be recycled up to five times without any significant loss in the product yield.
The use of a continuous flow-reactor employing a mixed hydrogen-liquid flow stream for the efficient reduction of imines to amines
Saaby, Steen,Knudsen, Kristian Rahbek,Ladlow, Mark,Ley, Steven V.
, p. 2909 - 2911 (2005)
Imines have been reduced to amines in high yield, and with excellent chemoselectivity, by catalytic hydrogenation in a continuous flow-reactor, utilising an electrochemically-generated hydrogen source to produce a mixed hydrogen-liquid flow stream. The Royal Society of Chemistry 2005.
Triazolylidene-Iridium Complexes with a Pendant Pyridyl Group for Cooperative Metal–Ligand Induced Catalytic Dehydrogenation of Amines
Valencia, Marta,Pereira, Ana,Müller-Bunz, Helge,Belderraín, Tomás R.,Pérez, Pedro J.,Albrecht, Martin
, p. 8901 - 8911 (2017)
Two iridium(III) complexes containing a C,N-bidentate pyridyl-triazolylidene ligand were prepared that are structurally very similar but differ in their pendant substituent. Whereas complex 1 contains a non-coordinating pyridyl unit, complex 2 has a phenyl group on the triazolylidene substituent. The presence of the basic pyridyl unit has distinct effects on the catalytic activity of the complex in the oxidative dehydrogenation of benzylic amines, inducing generally higher rates, higher selectivity towards formation of imines versus secondary amines, and notable quantities of tertiary amines when compared to the phenyl-functionalized analogue. The role of the pyridyl functionality has been elucidated from a set of stoichiometric experiments, which demonstrate hydrogen bonding between the pendant pyridyl unit and the amine protons of the substrate. Such Npyr???H?N interactions are demonstrated by X-ray diffraction analysis, 1H NMR, and IR spectroscopy, and suggest a pathway of substrate bond-activation that involves concerted substrate binding through the Lewis acidic iridium center and the Lewis basic pyridyl site appended to the triazolylidene ligand, in agreement with ligand–metal cooperative substrate activation.
Air Stable Iron(II) PNP Pincer Complexes as Efficient Catalysts for the Selective Alkylation of Amines with Alcohols
Mastalir, Matthias,St?ger, Berthold,Pittenauer, Ernst,Puchberger, Michael,Allmaier, Günter,Kirchner, Karl
, p. 3824 - 3831 (2016)
A series of well-defined iron(II) complexes of the types [Fe(PNP)Br2] and [Fe(PNP)(CO)Br2] with PNP pincer ligands based on triazine and pyridine backbones were prepared and fully characterized. These complexes were tested as catalysts for the alkylation of amines by alcohols. The high-spin complexes [Fe(PNP)Br2] are catalytically inactive. The low-spin complexes [Fe(PNP)(CO)Br2] bearing a carbonyl co-ligand efficiently and selectively convert primary alcohols and aromatic and benzylic amines selectively into mono-N-alkylated amines in good to excellent isolated yields. A mechanistic proposal is given. (Figure presented.).
