91-73-6Relevant academic research and scientific papers
Discriminating non-ylidic carbon-sulfur bond cleavages of sulfonium ylides for alkylation and arylation reactions
Fang, Jing,Li, Ting,Ma, Xiang,Sun, Jiuchang,Cai, Lei,Chen, Qi,Liao, Zhiwen,Meng, Lingkui,Zeng, Jing,Wan, Qian
, p. 288 - 292 (2021/07/25)
A sulfonium ylide participated alkylation and arylation under transition-metal free conditions is described. The disparate reaction pattern allowed the separate activation of non-ylidic S-alkyl and S-aryl bond. Under acidic conditions, sulfonium ylides serve as alkyl cation precursors which facilitate the alkylations. While under alkaline conditions, cleavage of non-ylidic S-aryl bond produces O-arylated compounds efficiently. The robustness of the protocols were established by the excellent compatibility of wide variety of substrates including carbohydrates.
Regioselective Synthesis of 2° Amides Using Visible-Light-Induced Photoredox-Catalyzed Nonaqueous Oxidative C-N Cleavage of N, N-Dibenzylanilines
Neerathilingam, Nalladhambi,Bhargava Reddy, Mandapati,Anandhan, Ramasamy
supporting information, p. 15117 - 15127 (2021/10/25)
A visible-light-driven photoredox-catalyzed nonaqueous oxidative C-N cleavage of N,N-dibenzylanilines to 2° amides is reported. Further, we have applied this protocol on 2-(dibenzylamino)benzamide to afford quinazolinones with (NH4)2S2O8 as an additive. Mechanistic studies imply that the reaction might undergo in situ generation of α-amino radical to imine by C-N bond cleavage followed by the addition of superoxide ion to form amides.
Aza-Matteson Reactions via Controlled Mono-and Double-Methylene Insertions into Nitrogen-Boron Bonds
Xie, Qiqiang,Dong, Guangbin
supporting information, p. 14422 - 14427 (2021/09/29)
Boron-homologation reactions represent an efficient and programmable approach to prepare alkylboronates, which are valuable and versatile synthetic intermediates. The typical boron-homologation reaction, also known as the Matteson reaction, involves formal carbenoid insertions into C-B bonds. Here we report the development of aza-Matteson reactions via carbenoid insertions into the N-B bonds of aminoboranes. By changing the leaving groups of the carbenoids and altering Lewis acid activators, selective mono- and double-methylene insertions can be realized to access various α- and β-boron-substituted tertiary amines, respectively, from common secondary amines. The derivatization of complex amine-containing bioactive molecules, diverse functionalization of the boronate products, and sequential insertions of different carbenoids have also been achieved.
Preparation method of N-alkylated derivative of primary amine compound
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Paragraph 0021; 0058, (2021/07/09)
The invention relates to a preparation method of an N-alkylated derivative of a primary amine compound. The method comprises the following steps: uniformly mixing a primary amine compound, an alcohol compound and a catalyst in a reactor, and heating to react for a period of time to generate an N-alkylated substituted tertiary amine compound; wherein the catalyst is a copper-cobalt bimetallic catalyst, and the carrier of the catalyst is Al2O3. According to the method, alcohol is adopted as an alkylating reagent and is low in price and easy to obtain, a byproduct is water, no pollution is caused to the environment, and the overall reaction atom economy is high; the catalyst is simple in preparation method, low in cost, high in reaction activity and good in structural stability; meanwhile, by using the copper-cobalt bimetallic catalyst, the use of strong base additives can be avoided, and the requirement on reaction equipment is low; and the reaction post-treatment is convenient, and the catalyst can be recycled and is environment-friendly.
Synthesis ofN-aryl amines enabled by photocatalytic dehydrogenation
Kim, Jungwon,Kim, Siin,Choi, Geunho,Lee, Geun Seok,Kim, Donghyeok,Choi, Jungkweon,Ihee, Hyotcherl,Hong, Soon Hyeok
, p. 1915 - 1923 (2021/02/22)
Catalytic dehydrogenation (CD)viavisible-light photoredox catalysis provides an efficient route for the synthesis of aromatic compounds. However, access toN-aryl amines, which are widely utilized synthetic moieties,viavisible-light-induced CD remains a significant challenge, because of the difficulty in controlling the reactivity of amines under photocatalytic conditions. Here, the visible-light-induced photocatalytic synthesis ofN-aryl amines was achieved by the CD of allylic amines. The unusual strategy using C6F5I as an hydrogen-atom acceptor enables the mild and controlled CD of amines bearing various functional groups and activated C-H bonds, suppressing side-reaction of the reactiveN-aryl amine products. Thorough mechanistic studies suggest the involvement of single-electron and hydrogen-atom transfers in a well-defined order to provide a synergistic effect in the control of the reactivity. Notably, the back-electron transfer process prevents the desired product from further reacting under oxidative conditions.
A Bottleable Imidazole-Based Radical as a Single Electron Transfer Reagent
Das, Arpan,Ahmed, Jasimuddin,Rajendran,Adhikari, Debashis,Mandal, Swadhin K.
, p. 1246 - 1252 (2020/12/21)
Reduction of 1,3-bis(2,6-diisopropylphenyl)-2,4-diphenyl-1H-imidazol-3-ium chloride (1) resulted in the formation of the first structurally characterized imidazole-based radical 2. 2 was established as a single electron transfer reagent by treating it with an acceptor molecule tetracyanoethylene. Moreover, radical 2 was utilized as an organic electron donor in a number of organic transformations such as in activation of an aryl-halide bond, alkene hydrosilylation, and in catalytic reduction of CO2 to methoxyborane, all under ambient temperature and pressure.
Effect of Precatalyst Oxidation State in C-N Cross-Couplings with 2-Phosphinoimidazole-Derived Bimetallic Pd(I) and Pd(II) Complexes
Martinez, Erin E.,Moreno, Mariur Rodriguez,Barksdale, Caleb A.,Michaelis, David J.
supporting information, p. 2763 - 2767 (2021/08/27)
We report the catalytic activity of two phosphinoimidazole-derived bimetallic palladium complexes in Pd-catalyzed amination reactions. Our studies demonstrate that the starting oxidation state (Pd(I) or Pd(II)) of the dimeric complex has a significant effect on the efficiency of the catalytic reaction. The corresponding Pd(I) complex shows higher reactivity in Buchwald-Hartwig aminations, while the Pd(II) complex is much more reactive in carbonylative amination reactions. These new dimeric palladium complexes provide good to excellent reactivity and yields in the amination reactions tested.
N-Benzylation of primary amines using magnetic Fe3O4 nanoparticles functionalized with hexamethylenetetramine as an efficient and recyclable heterogeneous catalyst
Ghorbani-Vaghei, Ramin,Mirzaei-Mosbat, Maryam,Noori, Samira
, (2020/06/22)
Herein we report, a new, simple and mild procedure for N-benzylation and N,N-dibenzylation of anilines through the reaction of aniline derivatives and benzyl bromide at 60 °C in EtOH in the presence of catalytic amounts of magnetic Fe3O4 nanoparticles functionalized with hexamethylenetetramine (Fe3O4?SiO2?Propyl-HMTA). The title compounds were formed in high purity and their structures characterized by spectral analysis. The results also showed that the magnetic nanoparticle catalyst had significant advantages including, simplicity of preparation, heterogeneity, stability and recyclability. Moreover, the catalyst was characterized by various methods, such as FT-IR, SEM, VSM, TEM, TGA and XRD, after the reaction to compare with its structure before reaction.
SULFONYL-SUBSTITUTED BICYCLIC COMPOUND WHICH ACTS AS ROR INHIBITOR
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Paragraph 0547; 0548, (2020/08/16)
Provided is a sulfonyl-substituted bicyclic compound (A) which acts as a RORγ inhibitor, said compound has good RORγ inhibitory activity and is expected to be used for treating diseases mediated by a RORγ receptor in mammals.
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.
