3963-62-0Relevant academic research and scientific papers
Direct Access to Primary Amines from Alkenes by Selective Metal-Free Hydroamination
Du, Yi-Dan,Chen, Bi-Hong,Shu, Wei
supporting information, p. 9875 - 9880 (2021/03/29)
Direct and selective synthesis of primary amines from easily available precursors is attractive yet challenging. Herein, we report the rapid synthesis of primary amines from alkenes via metal-free regioselective hydroamination at room temperature. Ammonium carbonate was used as ammonia surrogate for the first time, allowing for efficient conversion of terminal and internal alkenes into linear, α-branched, and α-tertiary primary amines under mild conditions. This method provides a straightforward and powerful approach to a wide spectrum of advanced, highly functionalized primary amines which are of particular interest in pharmaceutical chemistry and other areas.
General and selective synthesis of primary amines using Ni-based homogeneous catalysts
Beller, Matthias,Chandrashekhar, Vishwas G.,Jagadeesh, Rajenahally V.,Jiao, Haijun,Murugesan, Kathiravan,Wei, Zhihong
, p. 4332 - 4339 (2020/05/18)
The development of base metal catalysts for industrially relevant amination and hydrogenation reactions by applying abundant and atom economical reagents continues to be important for the cost-effective and sustainable synthesis of amines which represent highly essential chemicals. In particular, the synthesis of primary amines is of central importance because these compounds serve as key precursors and central intermediates to produce value-added fine and bulk chemicals as well as pharmaceuticals, agrochemicals and materials. Here we report a Ni-triphos complex as the first Ni-based homogeneous catalyst for both reductive amination of carbonyl compounds with ammonia and hydrogenation of nitroarenes to prepare all kinds of primary amines. Remarkably, this Ni-complex enabled the synthesis of functionalized and structurally diverse benzylic, heterocyclic and aliphatic linear and branched primary amines as well as aromatic primary amines starting from inexpensive and easily accessible carbonyl compounds (aldehydes and ketones) and nitroarenes using ammonia and molecular hydrogen. This Ni-catalyzed reductive amination methodology has been applied for the amination of more complex pharmaceuticals and steroid derivatives. Detailed DFT computations have been performed for the Ni-triphos based reductive amination reaction, and they revealed that the overall reaction has an inner-sphere mechanism with H2metathesis as the rate-determining step.
Ultra-small cobalt nanoparticles from molecularly-defined Co-salen complexes for catalytic synthesis of amines
Beller, Matthias,Chandrashekhar, Vishwas G.,Gawande, Manoj B.,Jagadeesh, Rajenahally V.,Kalevaru, Narayana V.,Kamer, Paul C. J.,Senthamarai, Thirusangumurugan,Zbo?il, Radek
, p. 2973 - 2981 (2020/03/27)
We report the synthesis of in situ generated cobalt nanoparticles from molecularly defined complexes as efficient and selective catalysts for reductive amination reactions. In the presence of ammonia and hydrogen, cobalt-salen complexes such as cobalt(ii)-N,N′-bis(salicylidene)-1,2-phenylenediamine produce ultra-small (2-4 nm) cobalt-nanoparticles embedded in a carbon-nitrogen framework. The resulting materials constitute stable, reusable and magnetically separable catalysts, which enable the synthesis of linear and branched benzylic, heterocyclic and aliphatic primary amines from carbonyl compounds and ammonia. The isolated nanoparticles also represent excellent catalysts for the synthesis of primary, secondary as well as tertiary amines including biologically relevant N-methyl amines.
Diprotonative stabilization of ring-opened carbocationic intermediates: conversion of tetrahydroisoquinoline to triarylmethanes
Kurouchi, Hiroaki
supporting information, p. 8313 - 8316 (2020/08/17)
Superacid-promoted conversion of tetrahydroisoquinolines to triarylmethanes via tandem reactions of C-N bond scission, Friedel-Crafts alkylation, C-O bond scission, and electrophilic aromatic amidation was developed. Dication formation was important for stabilizing the ring-opened carbocationic intermediate, which is a new role for diprotonation in reaction mechanisms. This journal is
Continuous-Flow Hydrogenation and Reductive Deuteration of Nitriles: a Simple Access to α,α-Dideutero Amines
Mészáros, Rebeka,Peng, Bai-Jing,?tv?s, Sándor B.,Yang, Shyh-Chyun,Fül?p, Ferenc
, p. 1508 - 1511 (2019/11/03)
A simple and efficient continuous flow methodology has been developed for hydrogenation and reductive deuteration of nitriles to yield primary amines and also valuable α,α-dideutero analogues. Raney nickel proved to be a useful catalyst for the transformation of a wide range of nitriles under reasonably mild conditions with excellent deuterium incorporation (>90 %) and quantitative conversion. Among known model compounds, three new deuterated primary amines were prepared. The large-scale synthesis of deuterated tryptamine was also carried out to deliver 1.1 g product under flow conditions.
Cobalt-based nanoparticles prepared from MOF-carbon templates as efficient hydrogenation catalysts
Murugesan, Kathiravan,Senthamarai, Thirusangumurugan,Sohail, Manzar,Alshammari, Ahmad S.,Pohl, Marga-Martina,Beller, Matthias,Jagadeesh, Rajenahally V.
, p. 8553 - 8560 (2018/11/30)
The development of efficient and selective nanostructured catalysts for industrially relevant hydrogenation reactions continues to be an actual goal of chemical research. In particular, the hydrogenation of nitriles and nitroarenes is of importance for the production of primary amines, which constitute essential feedstocks and key intermediates for advanced chemicals, life science molecules and materials. Herein, we report the preparation of graphene shell encapsulated Co3O4- and Co-nanoparticles supported on carbon by the template synthesis of cobalt-terephthalic acid MOF on carbon and subsequent pyrolysis. The resulting nanoparticles create stable and reusable catalysts for selective hydrogenation of functionalized and structurally diverse aromatic, heterocyclic and aliphatic nitriles, and as well as nitro compounds to primary amines (>65 examples). The synthetic and practical utility of this novel non-noble metal-based hydrogenation protocol is demonstrated by upscaling several reactions to multigram-scale and recycling of the catalyst.
Synthesis and characterization of copper nanoparticles on walnut shell for catalytic reduction and C-C coupling reaction
Zamani, Asghar,Poursattar Marjani, Ahmad,Nikoo, Abbas,Heidarpour, Mojtaba,Dehghan, Ahmad
, p. 176 - 181 (2018/09/25)
Walnut shell-stabilized copper nanoparticles (CuNP/WS) were successfully prepared by a simple reaction of copper sulfate and Sodium borohydride. Formation of copper nanoparticles in this bio-nanocomposite was observed by transmission electron microscopy (TEM) and energy dispersive X-ray spectroscope (EDX). CuNP/WS was found to be an efficient, inexpensive, easy to prepare, green and reusable catalyst in the reduction of aromatic nitro and nitrile compounds to their corresponding amines with NaBH4 at 35 °C in aqueous medium. We continued our studies on the application of this nanocomposite in the classic Ullman reaction to synthesize biaryl. This method has the advantages of high yields, elimination of expensive stabilizer and homogeneous catalysts, simple methodology and easy work up. The catalyst can be recovered from the reaction mixture and reused several times without any significant loss of catalytic activity.
MOF-derived cobalt nanoparticles catalyze a general synthesis of amines
Jagadeesh, Rajenahally V.,Murugesan, Kathiravan,Alshammari, Ahmad S.,Neumann, Helfried,Pohl, Marga-Martina,Radnik, J?rg,Beller, Matthias
, p. 326 - 332 (2017/09/28)
The development of base metal catalysts for the synthesis of pharmaceutically relevant compounds remains an important goal of chemical research. Here, we report that cobalt nanoparticles encapsulated by a graphitic shell are broadly effective reductive amination catalysts. Their convenient and practical preparation entailed template assembly of cobaltdiamine- dicarboxylic acid metal organic frameworks on carbon and subsequent pyrolysis under inert atmosphere.The resulting stable and reusable catalysts were active for synthesis of primary, secondary, tertiary, and N-methylamines (more than 140 examples).The reaction couples easily accessible carbonyl compounds (aldehydes and ketones) with ammonia, amines, or nitro compounds, and molecular hydrogen under industrially viable and scalable conditions, offering cost-effective access to numerous amines, amino acid derivatives, and more complex drug targets.
An efficient synthesis of substituted isoxazolopyrroloisoquinolines via diastereoselective N-acyliminium ion cyclization
Ledovskaya, Maria S.,Molchanov, Alexander P.,Boitsov, Vitaly M.,Kostikov, Rafael R.,Stepakov, Alexander V.
, p. 1952 - 1958 (2015/04/14)
A simple and efficient strategy was developed for the synthesis of fused pyrrolo[2,1-a]isoquinoline ring systems. The 5- and 6-substituted isoxazolopyrroloisoquinolines were readily prepared via diastereoselective N-acyliminium ion cyclization of 5-(1-R(or 2-R)-substituted-2-phenylethyl)-6-hydroxytetrahydro-4H-pyrrolo[3,4-d]isoxazol-4-ones derived from the corresponding bicyclic dihydroisoxazoles.
Silica-supported polyphosphoric acid in the synthesis of 4-substituted tetrahydroisoquinoline derivatives
Manolov, Stanimir,Nikolova, Stoyanka,Ivanov, Iliyan
, p. 1869 - 1880 (2013/04/10)
We report herein an application of an α-amidoalkylation reaction, as an alternative efficient synthesis of 4-aryl- and 4-methyl-1,2,3,4- tetrahydroisoquinoline derivatives. The amides required for this purpose would result from reaction of aminoacetaldehyde dimethylacetal with different substituted benzenes in polyphosphoric acid, followed by acylation of the obtained amines with different acid chlorides or sulfochlorides. We compared the cyclisation step using conventional (milieu of acetictrifluoracetic acid = 4:1) and solid supported reagents (SiO2/PPA), as recovered, regenerated and reused without loss of its activity catalyst. We found that in comparison to conventional methods, the yields of the reaction are greater and the reaction time is shorter.
