937-33-7Relevant academic research and scientific papers
C–N Cross-coupling Reactions of Amines with Aryl Halides Using Amide-Based Pincer Nickel(II) Catalyst
Albkuri, Yahya M.,RanguMagar, Ambar B.,Brandt, Andrew,Wayland, Hunter A.,Chhetri, Bijay P.,Parnell, Charlette M.,Szwedo, Peter,Parameswaran-Thankam, Anil,Ghosh, Anindya
, p. 1669 - 1678 (2019/12/27)
Abstract: An approach to C–N cross-coupling reactions of aryl halides with amines in the presence of an amide-based pincer nickel(II) catalyst (2) is described. For 3?h reactions at 110?°C with 0.2?mol% catalyst, aryl bromides gave higher turnover numbers (TON) than the corresponding chlorides or iodides. Both primary and secondary amines could be used with the former giving higher TON. However, sterically hindered amines showed lower TON. In elucidating the mechanism of this nickel complex-catalyzed C–N cross coupling reaction it was found that the rate of reaction was unchanged in the presence of radical quenchers and a plausible Ni(I)–Ni(III) pathway is proposed. Graphic Abstract: [Figure not available: see fulltext.]Nickel pincer catalyst proved to be excellent catalyst for the C-N cross-coupling reaction with the high turnover number (TON) for 1° and 2° amines and different nonactivated aryl halides under optimum conditions.
Practical and regioselective amination of arenes using alkyl amines
Ruffoni, Alessandro,Juliá, Fabio,Svejstrup, Thomas D.,McMillan, Alastair J.,Douglas, James J.,Leonori, Daniele
, p. 426 - 433 (2019/05/01)
The formation of carbon–nitrogen bonds for the preparation of aromatic amines is among the top five reactions carried out globally for the production of high-value materials, ranging from from bulk chemicals to pharmaceuticals and polymers. As a result of this ubiquity and diversity, methods for their preparation impact the full spectrum of chemical syntheses in academia and industry. In general, these molecules are assembled through the stepwise introduction of a reactivity handle in place of an aromatic C–H bond (that is, a nitro group, halogen or boronic acid) and a subsequent functionalization or cross-coupling. Here we show that aromatic amines can be constructed by direct reaction of arenes and alkyl amines using photocatalysis, without the need for pre-functionalization. The process enables the easy preparation of advanced building blocks, tolerates a broad range of functionalities, and multigram scale can be achieved via a batch-to-flow protocol. The merit of this strategy as a late-stage functionalization platform has been demonstrated by the modification of several drugs, agrochemicals, peptides, chiral catalysts, polymers and organometallic complexes.
PEt3-mediated deoxygenative C–N coupling of nitroarenes and boronic acids
Nykaza, Trevor V.,Yang, Junyu,Radosevich, Alexander T.
supporting information, p. 3248 - 3252 (2019/04/25)
A method for the preparation of aryl- and heteroarylamine products by triethylphosphine-mediated deoxygenative coupling of nitroarenes and boronic acids is reported. This method provides access to an array of functionalized (hetero)arylamine products from readily available starting materials under the action of an inexpensive commercial reagent. The developed triethylphosphine-mediated transformation highlights the capability of organophosphorus compounds to carry out this useful deoxygenative transformation without the necessity of any transition metal additives.
A Highly Active Ylide-Functionalized Phosphine for Palladium-Catalyzed Aminations of Aryl Chlorides
Weber, Philip,Scherpf, Thorsten,Rodstein, Ilja,Lichte, Dominik,Scharf, Lennart T.,Goo?en, Lukas J.,Gessner, Viktoria H.
supporting information, p. 3203 - 3207 (2019/01/09)
Ylide-functionalized phosphine ligands (YPhos) were rationally designed to fit the requirements of Buchwald–Hartwig aminations at room temperature. This ligand class combines a strong electron-donating ability comparable to NHC ligands with high steric demand similar to biaryl phosphines. The active Pd species are stabilized by agostic C?H???Pd rather than by Pd–arene interactions. The practical advantage of YPhos ligands arises from their easy and scalable synthesis from widely available, inexpensive starting materials. Benchmark studies showed that YPhos-Pd complexes are superior to the best-known phosphine ligands in room-temperature aminations of aryl chlorides. The utility of the catalysts was demonstrated by the synthesis of various arylamines in high yields within short reaction times.
Cu-Catalyzed Three-Component Carboamination of Alkenes
Gockel, Samuel N.,Buchanan, Travis L.,Hull, Kami L.
supporting information, p. 58 - 61 (2018/01/17)
Copper-catalyzed intermolecular carboamination of alkenes with α-halocarbonyls and amines is presented with 42 examples. Electron rich, electron poor, and internal styrenes, as well as α-olefins, are functionalized with α-halocarbonyls and aryl or aliphat
Synthesis of Polyfunctional Secondary Amines by the Reaction of Functionalized Organomagnesium Reagents with Tertiary Nitroalkanes
Dhayalan, Vasudevan,Knochel, Paul
, p. 3246 - 3256 (2015/10/19)
Addition of polyfunctionalized aryl, heteroaryl, and tertiary alkylmagnesium reagents to tertiary nitroalkanes at 25A"°C in tetrahydrofuran produces, after reductive workup with FeCl2 and NaBH4 in ethanol, the corresponding polyfunctional secondary amines in high yields.
Synthesis of polyfunctional secondary amines by the addition of functionalized zinc reagents to nitrosoarenes
Dhayalan, Vasudevan,S?mann, Christoph,Knochel, Paul
supporting information, p. 3239 - 3242 (2015/06/01)
Addition of functionalized aryl, heteroaryl or adamantyl zinc reagents to various nitroso-arenes in the presence of magnesium salts and LiCl in THF produces after a reductive work-up with FeCl2 and NaBH4 in ethanol the corresponding polyfunctional secondary amines in high yields. This journal is
Palladium-catalyzed amination of aryl sulfides with aliphatic amines
Gao, Ke,Yorimitsu, Hideki,Osuka, Atsuhiro
supporting information, p. 2678 - 2682 (2015/04/27)
Conditions for the palladium-NHC-catalyzed amination of aryl sulfides with aliphatic as well as aromatic amines were established. The KHMDS-mediated amination of heteroaryl sulfides could proceed without palladium. Based on the distinct difference in reactivity of C-Br and C-S bonds, a sequential amination of bromothioanisole can take place to install two different alkylamino groups onto the aromatic ring in one pot. A palladium-NHC precatalyst shows high efficiency for C-S bond cleavage for the amination of aryl sulfides with aliphatic amines or aromatic amines.
Ligand-free copper(i) oxide nanoparticle-catalysed amination of aryl halides in ionic liquids
Kessler, Michael T.,Robke, Silas,Sahler, Sebastian,Prechtl, Martin H. G.
, p. 102 - 108 (2014/01/06)
In the following, we present a simple and feasible methodology for a C-N coupling reaction using nanoscale Cu2O catalysts incorporated in n-Bu4POAc ionic liquid media. It is shown that a wide range of amines and aryl halides can be coupled selectively in high yields, without the use of ligands or additives (bases) and without precautions against water or air. All catalyses can be carried out with a nanoparticle catalyst loading as low as 5 mol%, based on the used precursor.
Copper-catalyzed N- tert -butylation of aromatic amines under mild conditions using tert -butyl 2,2,2-trichloroacetimidate
Cran, John W.,Vidhani, Dinesh V.,Krafft, Marie E.
, p. 1550 - 1554 (2014/07/08)
A variety of aromatic amines have been found to expediently undergo copper-catalyzed N-tert-butylation in the presence of tert-butyl 2,2,2-trichloroactimidate at room temperature. Georg Thieme Verlag Stuttgart New York.
