93948-20-0Relevant articles and documents
Chemoselective transfer hydrogenation of nitriles to secondary amines with nickel(II) catalysts
Vermaak, Vincent,Vosloo, Hermanus C.M.,Swarts, Andrew J.
, (2021/07/25)
Herein we report the selective transfer hydrogenation (TH) of nitriles to secondary (2°) amines with simple Ni(II)-catalysts using ammonia borane (AB) as a source of hydrogen (H2). A bis(pyrazolylmethyl)pyridine (L1) or ethylenediamine (L4) ligated Ni(II) pre-catalyst, created in situ, could hydrogenate several aromatic- and aliphatic nitriles in full conversions and isolated yields of up to 88% under ambient temperature and in very short reaction times. Deuterium labelling experiments illustrated the incorporation of a proton on the nitrogen and hydride on the α-carbon of dibenzylamine. Using α-picoline borane, containing no dissociable protons, assisted with the postulation of a two-step TH mechanism of benzonitrile. AB was subjected to dehydrogenation and it was observed that a maximum of 2.96 equivalents of H2 gas could be generated from NiCl2?6H2O/L1.
Sequential hydroaminomethylation/Pd-catalyzed hydrogenolysis as an atom efficient route to valuable primary and secondary amines
October, Jacquin,Mapolie, Selwyn F.
supporting information, (2021/04/12)
The facile synthesis of valuable primary and secondary amines is reported using a sequential procedure of hydroaminomethylation and Pd-catalyzed hydrogenolysis. The hydroaminomethylation reaction was catalyzed by a cationic Rh(I) iminopyridyl complex and the N-alkylated benzylamines were produced with high chemoselectivity, albeit as mixtures of linear and branched products. Performing the hydrogenolysis reaction using 10% Pd/C, provided access to valuable primary and secondary amines which have applications in the surfactant, pharmaceutical and polymer industries.
Pd/TiO2-Photocatalyzed Self-Condensation of Primary Amines to Afford Secondary Amines at Ambient Temperature
Wang, Lyu-Ming,Kobayashi, Kensuke,Arisawa, Mitsuhiro,Saito, Susumu,Naka, Hiroshi
supporting information, p. 341 - 344 (2018/12/11)
Symmetric secondary amines were synthesized by the self-condensation of primary amines over a palladium-loaded titanium dioxide (Pd/TiO2) photocatalyst. The reactions afforded a series of secondary amines in moderate to excellent isolated yields at ambient temperature (30 °C, in cyclopentyl methyl ether). Applicability for one-pot pharmaceutical synthesis was demonstrated by a photocatalytic reaction sequence of self-condensation of an amine followed by N-alkylation of the resulting secondary amine with an alcohol.
Chemoselective hydrogenation of nitriles to primary amines catalyzed by water-soluble transition metal catalysts
Nait Ajjou, Abdelaziz,Robichaud, André
, (2018/08/07)
The water-soluble rhodium complex generated in situ from [Rh (COD)Cl]2 in aqueous ammonia has been revealed as a highly efficient catalyst for the hydrogenation of aromatic nitriles, to primary amines with excellent yields. The catalyst is also highly selective towards primary amines in the case of sterically hindered aliphatic nitriles. The catalytic system can also be recycled and re-used with no significant loss of activity.
Conversion of Primary Amines to Symmetrical Secondary and Tertiary Amines using a Co-Rh Heterobimetallic Nanocatalyst
Chung, Hyunho,Han, Seulgi,Chung, Young Keun,Park, Ji Hoon
supporting information, p. 1267 - 1272 (2018/02/12)
Symmetrical tertiary amines have been efficiently realized from amine and secondary amines via deaminated homocoupling with heterogeneous bimetallic Co2Rh2/C as catalyst (molar ratio Co:Rh=2:2). Unsymmetric secondary anilines were produced from the reaction of anilines with symmetric tertiary amines. The Co2Rh2/C catalyst exhibited very high catalytic activity towards a wide range of amines and could be conveniently recycled ten times without considerable leaching. (Figure presented.).
An improved and one-pot procedure to the synthesis of symmetric amines by domino reactions of 5-methyl-1,3,4-thiadiazole-2-amine, a new nitrogen atom donor, and alkyl halides
Soleiman-Beigi, Mohammad,Mohammadi, Fariba
, p. 2123 - 2128 (2017/10/26)
Abstract: A new one-pot method has been introduced in this work for the synthesis of symmetrical primary, secondary, and tertiary alkyl amines from alkyl halides and 5-methyl-1,3,4-thiadiazole-2-amine as a nitrogen-transfer reagent. In this method, all three types of amines have been successfully prepared after changing the ratio of substrates and base control. In addition to the introduction of a new nitrogen-transfer reagent, other important features of this work include normal atmospheric conditions and excellent yields under mild reaction conditions.
Colloid and nanosized catalysts in organic synthesis: XIV. Reductive amination and amidation of carbonitriles catalyzed by nickel nanoparticles
Popov, Yu. V.,Mokhov,Shcherbakova
, p. 798 - 805 (2016/06/13)
Hydrogenation of carbonitriles catalyzed by nickel nanoparticles in the presence of primary amines led to the predominant formation of unsymmetrical secondary amines. In the presence of secondary amines hydrogenation of nitrites provided enamines as main products. Hydrogenation of nitriles in the presence of formamide or acetamide afforded formyl or acetyl derivatives of primary amines.
Colloid and nanosized catalysts in organic synthesis: XII. Hydrogenation of carbonitriles catalyzed by nickel nanoparticles
Mokhov,Popov,Shcherbakova
, p. 273 - 280 (2016/04/20)
Hydrogenation of carbonitriles catalyzed by nickel nanoparticles in isopropanol proceeds under atmospheric pressure of hydrogen within 6-15 h to yield mainly secondary amines. Hydrogenation of α-aminonitriles results in reductive decyanation. β-Aminonitriles undergo hydrogenolysis at the nitrogen-carbon bond.
Chemoselective hydrogenation of unsaturated nitriles to unsaturated primary amines: Conversion of cinnamonitrile on metal-supported catalysts
Segobia,Trasarti,Apesteguía
, p. 41 - 47 (2015/09/28)
The liquid-phase hydrogenation of cinnamonitrile to selectively obtain the unsaturated primary amine (cinnamylamine) was studied at 383 K and 13 bar on Ni, Co, Ru and Cu metals supported on a commercial silica. Ni/SiO2 and Co/SiO2 were the most active catalysts for cinnamonitrile conversion but formed only small amounts of cinnamylamine. In contrast, Cu/SiO2 and Ru/SiO2 presented low activity for cinnamonitrile hydrogenation but formed selectively cinnamylamine in the liquid phase; nevertheless, on both samples the carbon balance was only about 40%. In an attempt of promoting the rate and yield to cinnamylamine, additional catalytic runs were carried out at higher temperatures and H2 pressures on a highly dispersed Cu(11%)/SiO2 catalyst prepared by the chemisorption-hydrolysis method. Results showed that when cinnamonitrile hydrogenation was performed at 403 K and 40 bar on Cu(11%)/SiO2, the yield to cinnamylamine was 74% giving as by-product only the unsaturated secondary amine (dicinnamylamine).
A highly predictive 3D-QSAR model for binding to the voltage-gated sodium channel: Design of potent new ligands
Zha, Congxiang,Brown, George B.,Brouillette, Wayne J.
, p. 95 - 104 (2014/01/17)
A comprehensive comparative molecular field analysis (CoMFA) model for the binding of ligands to the neuronal voltage-gated sodium channel was generated based on 67 diverse compounds. Earlier published CoMFA models for this target provided μM ligands, but the improved model described here provided structurally novel compounds with low nM IC50. For example, new compounds 94 and 95 had IC50 values of 129 and 119 nM, respectively.
