cas 91-73-6, N,N-DIBENZYLANILINE | Articles data

Articles about 91-73-6Total 108 be found

Article title
Article abstract
Author
Journal number and time
Download

Discriminating non-ylidic carbon-sulfur bond cleavages of sulfonium ylides for alkylation and arylation reactions
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.
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)

Aza-Matteson Reactions via Controlled Mono-and Double-Methylene Insertions into Nitrogen-Boron Bonds
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.
Xie, Qiqiang,Dong, Guangbin
supporting information
p. 14422 - 14427
(2021/09/29)

Preparation method of N-alkylated derivative of primary amine compound
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.
-
Paragraph 0021; 0058

(2021/07/09)

Synthesis ofN-aryl amines enabled by photocatalytic dehydrogenation
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.
Kim, Jungwon,Kim, Siin,Choi, Geunho,Lee, Geun Seok,Kim, Donghyeok,Choi, Jungkweon,Ihee, Hyotcherl,Hong, Soon Hyeok
p. 1915 - 1923
(2021/02/22)

A Bottleable Imidazole-Based Radical as a Single Electron Transfer Reagent
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.
Das, Arpan,Ahmed, Jasimuddin,Rajendran,Adhikari, Debashis,Mandal, Swadhin K.
p. 1246 - 1252
(2020/12/21)

Effect of Precatalyst Oxidation State in C-N Cross-Couplings with 2-Phosphinoimidazole-Derived Bimetallic Pd(I) and Pd(II) Complexes
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.
Martinez, Erin E.,Moreno, Mariur Rodriguez,Barksdale, Caleb A.,Michaelis, David J.
supporting information
p. 2763 - 2767
(2021/08/27)

Regioselective Synthesis of 2° Amides Using Visible-Light-Induced Photoredox-Catalyzed Nonaqueous Oxidative C-N Cleavage of N, N-Dibenzylanilines
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.
Neerathilingam, Nalladhambi,Bhargava Reddy, Mandapati,Anandhan, Ramasamy
supporting information
p. 15117 - 15127
(2021/10/25)

Direct benzylation of amines with benzylic alcohols catalyzed by palladium/phosphine-borane catalyst system
Direct catalytic benzylation of amines with benzylic alcohols to give benzylamines has been newly developed by using palladium/phosphine-borane catalyst system. In this catalytic reaction, the linking between both phosphine and borane moieties in the ligand is very important. Hydroxy group of benzylic alcohols is activated by Lewis acidic borane to form a benzylpalladium intermediate which is attacked by amines to give benzylamine products.
Onodera, Gen,Kumagae, Hidenobu,Nakamura, Daiki,Hayasaki, Takuto,Fukuda, Tsutomu,Kimura, Masanari
supporting information

(2020/11/04)

Catalyst-free photodecarbonylation ofortho-amino benzaldehyde
It is almost a consensus that decarbonylation of the aldehyde group (-CHO) needs to not only be mediated by transition metal catalysts, but also requires severe reaction conditions (high temperature and long reaction time). In this work, inspired by the “conformational-selectivity-based” design strategy, we broke this consensus and discovered a catalyst-free photodecarbonylation of the aldehyde group. It revealed that decarbonylation can be easily achieved with visible light irradiation by introducing a tertiary amine into theortho-position of the aldehyde group. A diverse array of tertiary amines is tolerated by our photodecarbonylation under mild conditions. Furthermore, the (QM) computations of the mechanism and the experiments on well-designed special substrates revealed that our photodecarbonylation depends on the conformational specificity of the aldehyde group and tertiary amine, and occurs through an unusual [1,4]-H shift and a subsequent [1,3]-H shift.
Li, Lamei,Wang, Songping,Wei, Wentao,Yan, Ming,Zhou, Jingwei
supporting information
p. 3421 - 3426
(2020/06/25)

Nickel-Catalyzed Asymmetric Reductive 1,2-Carboamination of Unactivated Alkenes
Starting from diverse alkene-tethered aryl iodides and O-benzoyl-hydroxylamines, the enantioselective reductive cross-electrophilic 1,2-carboamination of unactivated alkenes was achieved using a chiral pyrox/nickel complex as the catalyst. This mild, modular, and practical protocol provides rapid access to a variety of β-chiral amines with an enantioenriched aryl-substituted quaternary carbon center in good yields and with excellent enantioselectivities. This process reveals a complementary regioselectivity when compared to Pd and Cu catalysis.
He, Jun,Xue, Yuhang,Han, Bo,Zhang, Chunzhu,Wang, You,Zhu, Shaolin
supporting information
p. 2328 - 2332
(2020/01/08)

N-Benzylation of primary amines using magnetic Fe3O4 nanoparticles functionalized with hexamethylenetetramine as an efficient and recyclable heterogeneous catalyst
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.
Ghorbani-Vaghei, Ramin,Mirzaei-Mosbat, Maryam,Noori, Samira
(2020/06/22)

SULFONYL-SUBSTITUTED BICYCLIC COMPOUND WHICH ACTS AS ROR INHIBITOR
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.
-
Paragraph 0547; 0548

(2020/08/16)

Photo-induced dealdehyding method
The invention provides a photo-induced dealdehyding method, and belongs to the technical field of organic synthesis. The photo-induced dealdehyding method comprises the following steps that a mixtureof a compound shown in the formula I and a solvent are reacted under an inert gas atmosphere and visible light irradiation, a dealdehyding product is obtained, and no photocatalyst is used in the whole process; wherein the structural formula of the formula I shown in the specification, R is a functional group and is selected from hydrogen, methyl, methoxyl, cyano, chlorine, bromine or fluorine. According to the photo-induced dealdehyding method, in the inert gas atmosphere, the compound shown in the formula (I) can be excited to generate carbon-oxygen bond homogeneous cracking through visiblelight irradiation, then free radical migration and double bond displacement are conducted, finally carbon monoxide is removed, aldehyde group removal is completed, no photocatalyst is needed in the whole process, operation is easy and convenient, and conditions are mild.
-
Paragraph 0048-0053; 0168-0173

(2020/06/16)

C–N Cross-coupling Reactions of Amines with Aryl Halides Using Amide-Based Pincer Nickel(II) Catalyst
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.
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)

Reaction of Nitrogen-Radicals with Organometallics Under Ni-Catalysis: N-Arylations and Amino-Functionalization Cascades
Herein, we report a strategy for the generation of nitrogen-radicals by ground-state single electron transfer with organyl–NiI species. Depending on the philicity of the N-radical, two types of processes have been developed. In the case of nucleophilic aminyl radicals direct N-arylation with aryl organozinc, organoboron, and organosilicon reagents was achieved. In the case of electrophilic amidyl radicals, cascade processes involving intramolecular cyclization, followed by reaction with both aryl and alkyl organometallics have been developed. The N-cyclization–alkylation cascade introduces a novel retrosynthetic disconnection for the assembly of substituted lactams and pyrrolidines with its potential demonstrated in the short total synthesis of four venom alkaloids.
Angelini, Lucrezia,Davies, Jacob,Simonetti, Marco,Malet Sanz, Laia,Sheikh, Nadeem S.,Leonori, Daniele
supporting information
p. 5003 - 5007
(2019/03/17)

Direct reductive coupling of nitroarenes and alcohols catalysed by Co-N-C/CNT@AC
A non-noble heterogeneous catalyst-a Co, N and C composite encapsulated carbon nanotube grown in situ on the surface of activated carbon (Co-N-C/CNT@AC)-was fabricated via the pyrolysis-reduction process. Co-N-C/CNT@AC catalyzed the reductive coupling of structurally diverse nitroarenes and alcohols to imines and secondary amines under exogenous base- and solvent-free conditions. BET, TEM, SEM, XRD and XPS characterization showed that the exceptional catalytic property of Co-N-C/CNT@AC could be explained by its nanostructure, Co-N and basic N species. Our protocol had advantages of low cost, environment-friendliness, and good applicability. Furthermore, a reaction route of nitroarenes, amines and alcohols as the starting materials was proposed to improve the atom economy of the reductive coupling of nitroarenes with alcohols.
Liu, Di,Yang, Ping,Zhang, Hao,Liu, Minjie,Zhang, Wenfei,Xu, Dongmei,Gao, Jun
p. 2129 - 2137
(2019/04/27)

Iridium-Catalyzed Alkylation of Amine and Nitrobenzene with Alcohol to Tertiary Amine under Base- and Solvent-Free Conditions
Herein, an efficient and green method for the selective synthesis of tertiary amines has been developed that involves iridium-catalyzed alkylation of various primary amines with aromatic or aliphatic alcohols. Notably, the catalytic protocol enables this transformation in the absence of additional base and solvent. Furthermore, the alkylation of nitrobenzene with primary alcohol to tertiary amine has also been achieved by the same catalytic system. Deuterium-labeling experiments and a series of control experiments were conducted, and the results suggested that an intermolecular borrowing hydrogen pathway might exist in the alkylation process.
Li, Chao,Wan, Ke-Feng,Guo, Fu-Ya,Wu, Qian-Hui,Yuan, Mao-Lin,Li, Rui-Xiang,Fu, Hai-Yan,Zheng, Xue-Li,Chen, Hua
p. 2158 - 2168
(2019/05/16)

Tertiary amine synthesis method
The invention relates to the technical field of organic matters, and specifically relates to a tertiary amine synthesis method. Under the action of a catalyst, in the absence of solvent and alkali, primary amine, secondary amine, or a nitro derivative reacts with alcohol to prepare tertiary amine. The provided synthesis method has the advantages that no toxic solvent is used during the preparationprocess, the method is green and environmentally friendly, the atom utilization rate is high, the operation is simple, the application range of the functional groups and substrate is wide, and the yield of tertiary amine is high, in particular reactions between aliphatic amine and alcohol.
-
Paragraph 0027-0031

(2019/01/24)

N-Alkylation of Aniline and Its Derivatives by Alcohols in the Presence of Copper Compounds
N-Alkyl- and N,N-dialkyl-substituted anilines were obtained in the reaction of aniline and its derivatives with primary and secondary alcohols in the presence of catalysts CuCl2·2H2O, CuBr2 and halomethanes as promoters.
Bayguzina,Musina, Ch. F.,Khusnutdinov
p. 1652 - 1659
(2019/02/12)

Potassium tert-butoxide-mediated generation of arynes from o-bromoacetophenone derivatives
o-bromoacetophenone derivatives as new versatile aryne precursors are induced to selectively eliminate the CAr–Br and CAr–C(Ac) bonds in the help of t-BuOK. Furthermore, the active aryne intermediates are successfully appl
Chang, Denghu,Gao, Fei,Shi, Lei
p. 2428 - 2434
(2018/04/24)

Palladium-catalyzed amination of aryl sulfoxides
Amination of diaryl sulfoxides with anilines and alkylamines has been accomplished under palladium/N-heterocyclic carbene (NHC) catalysis. Owing to its electron deficiency, the leaving arenesulfenate anion would be smoothly released from the palladium center to result in uneventful catalyst turnover under milder reaction conditions in comparison with previous C-S bond amination reactions. This amination accommodated a wider range of functional groups such as silyl, boryl, methylsulfanyl, and halogen moieties. Regioselective amination of unsymmetrical diaryl sulfoxides was also executed by means of steric bias.
Yoshida, Yuto,Otsuka, Shinya,Nogi, Keisuke,Yorimitsu, Hideki
supporting information
p. 1134 - 1137
(2018/02/23)

MIL-101(Cr) as a synergistic catalyst for the reduction of imines with trichlorosilane
The development of catalyst based on porous crystalline materials (PCM) constructed from metal ions or clusters and multidentate organic ligands is a topic of great interest. In view of the Lewis acidic and basic properties of PCMs, we report for the first time that MIL-101(Cr) works as a synergistic catalyst for the reduction of imines with trichlorosilane as the hydrogen source. Both ketimines and aldimines were tolerated with this protocol, giving the corresponding amines in moderate to high yields. The operational simplicity as well as mild reaction conditions renders this protocol an attractive approach for the synthesis of amines. Furthermore, a chiral MOF, CMIL-101, was also realized by grafting chiral N-formyl proline derivatives to the open metal sites. Moreover, CMIL-101 exhibited a comparable catalytic performance with its homogeneous counterpart in terms of yields and enantioselectivities.
Chen, Jingwen,Chen, Xiaoling,Zhang, Zhiguo,Bao, Zongbi,Xing, Huabin,Yang, Qiwei,Ren, Qilong
p. 163 - 169
(2018/01/05)

Ruthenium nanoparticle catalyzed selective reductive amination of imine with aldehyde to access tertiary amines
Reductive amination is one of the most frequently used transformations in organic synthesis. Herein, we developed a novel ruthenium nanoparticle embedded ordered mesoporous carbon catalyst (Ru-OMC) and a new hydrosilylation process for the synthesis of tertiary amines. We present a direct reductive amination of imines (CN bond) with aldehydes (CO bond) using hydrosilane as the reducing reagent under mild conditions. Moreover, the Ru-OMC catalysts can be reused for up to 14 runs without noticeably losing activity.
Li, Bin,Liu, Shun,Lin, Qiao,Shao, Yan,Peng, Shiyong,Li, Yibiao
supporting information
p. 9214 - 9217
(2018/08/23)

Nickel Dual Photoredox Catalysis for the Synthesis of Aryl Amines
In this work, a new dual photoredox nickel catalysis system has been utilized for the synthesize of aryl amines. Previously, our group has shown that a nickel catalyst in conjunction with a photosensitizer and a sacrificial electron donor can cross-couple C-C bonds via photoredox-assisted reductive coupling. Here we have built upon that system to develop a redox-neutral cross-coupling system for the formation of C-N bonds. The catalytic system is composed of just a nickel cross-coupling catalyst, a Ru photocatalyst, and base and is capable of coupling amines with aryl halides in good to excellent yields. Furthermore, it was found that these reactions are functional under ambient conditions with catalyst loadings of 1 mol %. Spectroscopic studies provide support that this amination mechanism proceeds via a nitrogen-based radical intermediate. This N-radical mechanism offers direct synthetic access to di- and triaryl amines from nickel photocatalysis.
Key, Ryan J.,Vannucci, Aaron K.
p. 1468 - 1472
(2018/05/23)

Buchwald-Hartwig amination reaction of aryl halides using heterogeneous catalyst based on Pd nanoparticles decorated on chitosan functionalized graphene oxide
In this work, graphene oxide was functionalized with chitosan (GO-Chit) followed by a simple approach for immobilization of palladium nanoparticles onto a chitosan grafted graphene oxide surface. The Pd-nanocomposite (GO-Chit-Pd) was characterized using Transmission Electron Microscopy (TEM), Fourier transforms infrared spectroscopy (FT-IR), and X-ray diffraction (XRD) measurements. The catalytic activity of the prepared heterogeneous graphene oxide functionalized chitosan-palladium (GO-Chit-Pd) was investigated in term of C-N coupling reaction (Buchwald-Hartwig amination reaction of aryl halides) yielding products of N-arylamines. The easy purification, convenient operation, and environmental friendliness, combined with a high yield, render this method viable for use in both laboratory research and larger industrial scales. Studying the reusability of the catalyst in this work showed that it could be reused for five times without obvious loss in catalytic activity.
Sarvestani, Mosayeb,Azadi, Roya
(2017/10/05)

Unexpected Rearrangement of 2-Bromoaniline under Biphasic Alkylation Conditions
Alkylation of 2-bromoaniline with benzyl bromide under ostensibly basic N-alkylation conditions resulted in migration of bromine from the 2- to the 4-aryl position. Herein we report our studies to elucidate the mechanism of this rearrangement with the objective of suppressing this unexpected outcome. We find that careful choice of reagents is critical, and that this behavior may be extrapolated to alkylation reactions of electron-rich bromo- and iodoanilines in general.
Barraza, Scott J.,Denmark, Scott E.
supporting information
p. 2891 - 2895
(2017/10/06)

B(C6F5)3-Catalyzed Regioselective Deuteration of Electron-Rich Aromatic and Heteroaromatic Compounds
Deuterium labeled compounds find widespread application in life science. Herein, the deuteration of electron-rich (hetero)aromatic compounds employing B(C6F5)3 as the catalyst and D2O as the deuterium source is reported. This protocol is highly efficient, simply manipulated, and successfully applied in the deuteration of 23 substrates including natural neurotransmitter-like melatonin. It is assumed that the weakening of the O-D bond ultimately results in the formation of electrophilic D+.
Li, Wu,Wang, Ming-Ming,Hu, Yuya,Werner, Thomas
supporting information
p. 5768 - 5771
(2017/11/10)

Oxidation-Reduction Condensation of Diazaphosphites for Carbon-Heteroatom Bond Formation Based on Mitsunobu Mechanism
An efficient oxidation-reduction condensation reaction of diazaphosphites with various nonacidic pronucleophiles in the presence of DIAD as a weak oxidant has been developed for carbon-heteroatom bond formation. This mild process affords structurally diverse tertiary amines, secondary amines, esters, ethers, and thioethers in moderate to excellent yields. The selective synthesis of secondary amines from primary amines has been achieved. Importantly, a practical application to the synthesis of antiparkinsonian agent piribedil has been demonstrated.
Huang, Hai,Kang, Jun Yong
supporting information
p. 544 - 547
(2017/02/10)

Mitsunobu Reaction Using Basic Amines as Pronucleophiles
A novel protocol for extending the scope of the Mitsunobu reaction to include amine nucleophiles to form C-N bonds through the utilization of N-heterocyclic phosphine-butane (NHP-butane) has been developed. Both aliphatic alcohols and benzyl alcohols are suitable substrates for C-N bond construction. Various acidic nucleophiles such as benzoic acids, phenols, thiophenol, and secondary sulfonamide also provide the desired products of esters, ethers, thioether, and tertiary sulfonamide with 43-93% yields. Importantly, C-N bond-containing pharmaceuticals, Piribedil and Cinnarizine, have been synthesized in one step from the commercial amines under this Mitsunobu reaction system.
Huang, Hai,Kang, Jun Yong
p. 6604 - 6614
(2017/07/15)

“One pot” synthesis of tertiary amines: Ru(II) catalyzed direct reductive N-benzylation of imines with benzyl bromide derivatives
The direct reductive N-benzylation of imines by reaction with benzyl bromide derivatives, in the presence of [RuCl2(p-cymene)]2catalyst and PhSiH3, is performed under mild conditions without additional base. This reaction proceeds by a tandem imine hydrosilylation/nucleophilic substitution with benzyl bromide derivatives to result the tertiary amines.
Li, Bin,Yu, Jinghao,Li, Caihua,Li, Yibiao,Luo, Jianli,Shao, Yan
supporting information
p. 137 - 141
(2016/12/26)

A by a process for preparing amine derivatives of green method (by machine translation)
The invention discloses a by a process for preparing amine derivatives of green method, dumping with amine compound in a non-transition metal catalyst under solvent-free conditions and through the controllable high selection dehydration alkylation reaction different amine derivatives, a non-transition metal catalyst is a halogenated hydrocarbon, halogenated hydrocarbon in an amount of 1 - 50 μM %, under the catalysis of the mellow and amine in halogenated hydrocarbon can be directly performed by the amine derivative dehydration reaction, the reaction temperature is 100 - 180 °C, the reaction time is 12 - 48 hours, the by-product is water, the reaction needs to be carried out under the protection of inert gas, simple conditions, easy to operate, the by-product is water, the reaction selectivity is controllable, the target high selectivity. Requirements for reaction condition of relatively low, primary and secondary alcohol can be used for the alkylation reagent, is suitable for the dehydration of the primary and secondary amines single alkylation reaction, is also suitable for the dehydration of the double alkylation reaction of a primary amine, with wider scope, should also has certain research and industrial application prospect. (by machine translation)
-
Paragraph 0120 - 0123

(2017/08/14)

Scalable synthesis of secondary and tertiary amines by heterogeneous Pt-Sn/γ-Al2O3catalyzed N-alkylation of amines with alcohols
Synthesis of secondary and tertiary amines has been efficiently realized from the N-alkylation of amines with alcohols by means of heterogeneous bimetallic Pt-Sn/γ-Al2O3catalyst (0.5?wt % Pt, molar ratio Pt:Sn?=?1:3) through a borrowing hydrogen strategy. The Pt-Sn/γ-Al2O3catalyst has exhibited very high catalytic activity towards a wide range of amines and alcohols, and can be conveniently recycled without Pt metal leaching. The present protocol was applied for the synthesis of N-phenylbenzylamine in 96% isolated yield from aniline and benzyl alcohol on a 2.1?kg scale of the substrates, demonstrating its potential applicability for higher-order amine synthesis.
Wu, Kaikai,He, Wei,Sun, Chenglin,Yu, Zhengkun
p. 8516 - 8521
(2016/11/28)

Selective catalytic Hofmann: N -alkylation of poor nucleophilic amines and amides with catalytic amounts of alkyl halides
Using only catalytic amounts of alkyl halides in the reactions of poor nucleophilic amines/amides and alcohols led to a selective Hofmann N-alkylation reaction catalytic in alkyl halides, providing a practical and efficient method for the practical synthesis of mono- or di-alkylated amines/amides in high selectivities. This new method avoids the use of large amounts of bases, alkyl halides, and solvents, and generates water as the only byproduct. Preliminary mechanistic studies showed that alkyl halides are key intermediates/catalysts regeneratable in the reaction cycle.
Xu, Qing,Xie, Huamei,Zhang, Er-Lei,Ma, Xiantao,Chen, Jianhui,Yu, Xiao-Chun,Li, Huan
supporting information
p. 3940 - 3944
(2016/07/21)

Copper-catalyzed electrophilic amination using: N -methoxyamines
Copper-catalyzed electrophilic amination of a triarylboroxin using an N-methoxyamine to give quick access to a variety of anilines was reported. The reaction was especially useful for syntheses of functionalized anilines when combined with our previously reported nucleophilic addition to N-methoxyamides.
Fukami, Yutaro,Wada, Takamasa,Meguro, Tatsuhiko,Chida, Noritaka,Sato, Takaaki
supporting information
p. 5486 - 5489
(2016/07/06)

SILICON-BASED CROSS COUPLING AGENTS AND METHODS OF THEIR USE
Compositions and methods using silicon-based cross-coupling agents in the formation of carbon-carbon and carbon-nitrogen bonds are described.
-
Paragraph 0070

(2016/02/10)

A Bis(silylene)-Substituted ortho-Carborane as a Superior Ligand in the Nickel-Catalyzed Amination of Arenes
The synthesis and structure of the first 1,2-bis(NHSi)-substituted ortho-carborane [(LSi:)C]2B10H10(termed SiCCSi) is reported (NHSi=N-heterocyclic silylene; L=PhC(NtBu)2). Its suitability to serve as a reliable bis(silylene) chelating ligand for transition metals is demonstrated by the formation of [SiCCSi]NiBr2and [SiCCSi]Ni(CO)2complexes. The CO stretching vibration modes of the latter indicate that the SiIIatoms in the SiCCSi ligand are even stronger σ donors than the PIIIatoms in phosphines and CIIatoms in N-heterocyclic carbene (NHC) ligands. Moreover, the strong donor character of the [SiCCSi] ligand enables [SiCCSi]NiBr2to act as an outstanding precatalyst (0.5 mol % loading) in the catalytic aminations of arenes, surpassing the activity of previously known molecular Ni-based precatalysts (1–10 mol %).
Zhou, Yu-Peng,Raoufmoghaddam, Saeed,Szilvási, Tibor,Driess, Matthias
supporting information
p. 12868 - 12872
(2016/10/04)

Direct N-alkylation of aromatic amines using a microflow reactor: Enhancement of selectivity and reactivity
A simple and highly atom-economical method for the direct N-alkylation of aromatic amines by using a microflow reactor was developed to overcome the problem of over-alkylation. In the developed method, high-yield conversion (up to 100%) was achieved in a relatively short reaction time. The ratio of mono- to di-benzylated products (3.57:1) was higher than that achieved with batch reactions conducted in a 1 L scale flask (0.87:1). The structural features of the microflow reactor meant that short-chain alkyl halides could be converted into products with high reactivity and selectivity under superheating conditions, although their boiling point was much lower than the reaction temperature. This method was successfully applied to the synthesis of a range of secondary amines including an intermediate of indobufen synthesis.
Choi, Yong-Sung,Kim, Yoon-Jung,Shen, Liu-Lan,Lee, Yong Sup,Jeong, Jin-Hyun
supporting information
p. 970 - 974
(2015/04/27)

Metal-free reductive amination of aldehydes for the synthesis of secondary and tertiary amines
Reductive amination of aldehydes to produce secondary amines at room-temperature by in situ generated benzimidazoline is discussed. The bonus of the reaction is the formation of pharmaceutically important benzimidazole as a by-product in good yield, which can be recovered from the reaction mixture by simple filtration. The product, secondary amine, is transformed to tertiary amine in the same pot.
Ambica,Khajuria, Rajni,Saini, Yeshwinder,Kapoor, Kamal K
p. 1252 - 1259
(2015/11/25)

Copper-Catalyzed Electrophilic Amination of Organoaluminum Nucleophiles with O -Benzoyl Hydroxylamines
A copper-catalyzed electrophilic amination of aryl and heteroaryl aluminums with N,N-dialkyl-O-benzoyl hydroxylamines that affords the corresponding anilines in good yields has been developed. The catalytic reaction proceeds very smoothly under mild conditions and exhibits good substrate scope. Moreover, the developed catalytic system is also well suited for heteroaryl aluminum nucleophiles, providing facile access to heteroaryl amines.
Zhou, Shuangliu,Yang, Zhiyong,Chen, Xu,Li, Yimei,Zhang, Lijun,Fang, Hong,Wang, Wei,Zhu, Xiancui,Wang, Shaowu
p. 6323 - 6328
(2015/06/30)

PROCESS FOR FORMING PRIMARY, SECONDARY OR TERTIARY AMINE VIA DIRECT AMINATION REACTION
Disclosed is a process for preparing a primary, a secondary or a tertiary amine via the direct amination of an alcohol in the presence of a catalyst. The catalyst is composed of palladium or a palladium compound and a cerium oxide supporter.
-
Page/Page column 20-22

(2015/05/05)

Method of producing higher amine (by machine translation)
PROBLEM TO BE SOLVED: To provide a method of producing a secondary or tertiary higher amine. SOLUTION: The method of producing a higher amine comprises allowing a primary or secondary amine to react with an alcohol in the presence of at least one species of hydrogen halide selected from hydrogen chloride, hydrogen bromide and hydrogen iodide, or in the presence of a compound capable of producing a hydrogen halide (such as 1,3,5-triazo-2,4,6-triphosphorine-2,2,4,4,6,6-chloride). If the raw material amine is a primary amine, a secondary higher amine and a tertiary higher amine can be produced. If the raw material amine is a secondary amine, a tertiary higher amine can be produced. COPYRIGHT: (C)2012,JPO&INPIT
-
Paragraph 0048; 0073; 0083

(2016/10/08)

Synthesis of unsymmetric tertiary amines via alcohol amination
The first one-pot selective synthesis of unsymmetric tertiary amines is reported by the amination of two types of alcohols with primary amines via the development of a simple CuAlOx-HT catalyst and enables the synthesis of unsymmetric amines in a wide variety of primary amines and alcohols.
Pang, Shaofeng,Deng, Youquan,Shi, Feng
supporting information
p. 9471 - 9474
(2015/06/08)

Tunable dehydrogenative amidation versus amination using a single ruthenium-NHC catalyst
Mixed N-heterocyclic carbene (NHC)/phosphine complexes of the type [RuCl(p-cymene)(bimy)(PPh3)]- PF6 (bimy = benzimidazolin-2-ylidene) have been synthesized and fully characterized. Complex 1 bearing the 1,3-dibenzylbenzimidazolin-2-ylidene ligand is able to selectively catalyze both dehydrogenative amidation, mono-, and diamination (N-alkylation) through coupling of simple alcohols with amines effectively yielding a range of amides and secondary and tertiary amines. Selectivity is achieved by controlling the fate of the common hemiaminal intermediate, which in turn can be simply influenced by the choice of base and solvent.
Xie, Xiaoke,Huynh, Han Vinh
p. 4143 - 4151
(2015/11/11)

Concise synthesis of aromatic tertiary amines via a double Petasis-borono Mannich reaction of aromatic amines, formaldehyde, and organoboronic acids
A simple and efficient strategy to construct aromatic tertiary amines via a double Petasis-borono Mannich reaction of aromatic amines, formaldehyde, and organoboronic acids has been developed. The transformation provides a useful method for the synthesis of amine derivatives.
Wang, Jiayi,Li, Pinzhen,Shen, Qiaoying,Song, Gonghua
supporting information
p. 3888 - 3891
(2014/07/08)

Solvent free acid catalysed direct N-alkylation of amines with alcohols using Al grafted MCM-41
The catalytic activity of Al grafted MCM-41 (Al-MS) was explored for solvent free acid catalysed direct N-alkylation of amines using alcohols as green alkylating agent to establish a clean method for synthesis of N-alkylated amines. The study revealed that acidity of Al-MS catalyst, reaction conditions and substrate's (amines and alcohols) nature are important factors influencing the N-alkylation reaction. The Al grafted MCM-41 with Si/Al molar ratio of 5 showed excellent activity for N-alkylation of amines with alcohols. The reusability of spent catalyst regenerated by simple washing with acetone was demonstrated for subsequent four reaction cycles.
Tayade, Kamlesh N.,Mishra, Manish,Munusamy,Somani, Rajesh S.
p. 91 - 96
(2014/06/24)

Nano Pd-Fe3O4@Alg beads: As an efficient and magnetically separable catalyst for Suzuki, Heck and Buchwald-Hartwig coupling reactions
Catalytic processes are the backbone of many chemical industries. In a comparative study of various heterogeneous catalytic systems, we report efficient and magnetically separable nano Pd-Fe3O4@Alg beads as catalysts for Suzuki, Heck and Buchwald-Hartwig coupling reactions. This catalyst was characterized by SEM, TEM, HRTEM, XRD, EDAX, FT-IR, VSM, DSC-TGA, BET, and UV-Visible spectroscopy. This heterogeneous catalyst showed high catalytic activity and stability for C-C and C-N bond forming coupling reactions with excellent product yield under ligand free conditions. The beads of nano Pd-Fe3O4@Alg can be separated from the reaction mixture by an external magnet and reused for several successive cycles with no appreciable loss in the catalytic activity. The Suzuki and Heck coupling reactions in aqueous medium are greener routes, which is an added advantage of this protocol. This journal is
Shelkar, Radheshyam S.,Gund, Sitaram H.,Nagarkar, Jayashree M.
p. 53387 - 53396
(2015/02/05)

An expeditious N,N-dibenzylation of anilines under ultrasonic irradiation conditions using low loading Cu(II)-clay heterogeneous catalyst
A simple one-pot procedure for the direct N,N-dibenzylation of anilines using a catalytic amount of Cu modified montmorillonite-KSF is described. Cu modified montmorillonite-KSF has been proven to be a simple, efficient, mild, convenient, and effective catalyst for the selective benzylation of anilines with benzyl bromide. Cu loading plays a significant role in product yield and solvents were found to control the selectivity. The catalyst is easy to prepare, heterogeneous, stable, and easy to recover.
Dar, Bashir Ahmad,Shrivastava, Varsha,Bowmik, Amrita,Wagay, Mohammad Arif,Singh, Baldev
p. 136 - 141
(2015/02/02)

Nickel-catalyzed cross-coupling of aryltrimethylammonium triflates and amines
Nickel-catalyzed cross-coupling of aryltrimethylammonium triflates and amines was carried out under mild conditions. The reaction has a broad scope of substrates and can be performed by a one-pot procedure from an aryldimethylamine.
Zhang, Xue-Qi,Wang, Zhong-Xia
p. 1448 - 1453
(2014/03/21)

Reinvestigating Raney nickel mediated selective alkylation of amines with alcohols via hydrogen autotransfer methodology
An efficient, cost-effective use of Raney nickel (R-Ni) a widely used industrial catalyst for N-alkylation using alcohols is highlighted here. The work describes the scope and capability of R-Ni in hydrogen autotransfer reactions enabling its widespread use in the Chemical and Pharmaceutical industry. R-Ni of W4, T4, and W7 grades were prepared and evaluated for alkylation of amines. The best activity and selectivity for mono alkylation of amines were obtained using W4 R-Ni at 1:4 moles of amine to alcohol in xylene at reflux. T4 R-Ni also showed ability to form stable imines. The prepared R-Ni was also recycled and reused for N-alkylation reaction. The optimized methodology was applied for synthesis of Active Pharmaceutical ingredients Piribedil and Mepyramine. The simplicity and wide substrate scope makes this method a preferred Hydrogen Auto-transfer protocol for the alkylation of amines.
Mehta, Astha,Thaker,Londhe,Nandan, Santosh R.
p. 241 - 251
(2014/05/20)

N-alkylation of amines by homogeneous ruthenium complexes in the presence of free diphosphines
Chemoselective N-alkylation of amines by ruthenium complexes in the presence of free diphosphine ligands under mild conditions is described. Octyl amine and aniline were chosen as aliphatic and aromatic amines to investigate the effect of different phosphines, reaction times, and temperature on conversion, as well as selectivity towards related secondary and tertiary amines. After optimization of the reaction conditions, this catalytic system was used for N-alkylation of other amines and has shown moderate to very good yields. The reaction products were monitored by GC-MS. The crystal structure of [Ru(NO3)2CO(PPh3)2] with a monodentate and a bidentate nitrate was determined by X-ray crystallographic analysis.
Tamaddoni Jahromi, Bahareh,Kharat, Ali Nemati
p. 3498 - 3508
(2014/01/06)