cas 4714-62-9, 4-(N-Methylamino)benzonitrile

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A Mononuclear Non-heme Manganese(III)-Aqua Complex as a New Active Oxidant in Hydrogen Atom Transfer Reactions
A mononuclear non-heme Mn(III)-aqua complex, [(dpaq)MnIII(OH2)]2+ (1, dpaq = 2-[bis(pyridin-2-ylmethyl)]amino-N-quinolin-8-yl-acetamidate), is capable of conducting hydrogen atom transfer (HAT) reactions much more efficiently than the corresponding Mn(III)-hydroxo complex, [(dpaq)MnIII(OH)]+ (2); the high reactivity of 1 results from the positive one-electron reduction potential of 1 (Ered vs SCE = 1.03 V), compared to that of 2 (Ered vs SCE = -0.1 V). The HAT mechanism of 1 varies between electron transfer followed by proton transfer and one-step concerted proton-coupled electron transfer, depending on the one-electron oxidation potentials of substrates. To the best of our knowledge, this is the first example showing that metal(III)-aqua complex can be an effective H-atom abstraction reagent.
Sankaralingam, Muniyandi,Lee, Yong-Min,Karmalkar, Deepika G.,Nam, Wonwoo,Fukuzumi, Shunichi
p. 12695 - 12699
(2018)
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Reusable Co-nanoparticles for general and selectiveN-alkylation of amines and ammonia with alcohols
A general cobalt-catalyzedN-alkylation of amines with alcohols by borrowing hydrogen methodology to prepare different kinds of amines is reported. The optimal catalyst for this transformation is prepared by pyrolysis of a specific templated material, which is generatedin situby mixing cobalt salts, nitrogen ligands and colloidal silica, and subsequent removal of silica. Applying this novel Co-nanoparticle-based material, >100 primary, secondary, and tertiary amines includingN-methylamines and selected drug molecules were conveniently prepared starting from inexpensive and easily accessible alcohols and amines or ammonia.
Beller, Matthias,Gawande, Manoj B.,Jagadeesh, Rajenahally V.,Kadam, Ravishankar G.,Li, Xinmin,Ma, Zhuang,Petr, Martin,Zbo?il, Radek,Zhou, Bei
p. 111 - 117
(2022/01/06)

A nonheme peroxo-diiron(iii) complex exhibiting both nucleophilic and electrophilic oxidation of organic substrates
The complex [FeIII2(μ-O2)(L3)4(S)2]4+(L3= 2-(4-thiazolyl)benzimidazole, S = solvent) forms upon reaction of [FeII(L3)2] with H2O2and is a functional model of peroxo-diiron intermediates invoked during the catalytic cycle of oxidoreductases. The spectroscopic properties of the complex are in line with those of complexes formed with N-donor ligands. [FeIII2(μ-O2)(L3)4(S)2]4+shows both nucleophilic (aldehydes) and electrophilic (phenol,N,N-dimethylanilines) oxidative reactivity and unusually also electron transfer oxidation.
Browne, Wesley R.,Giorgi, Michel,Kaizer, József,T?r?k, Patrik,Unjaroen, Duenpen,Viktória Csendes, Flóra
supporting information
p. 7181 - 7185
(2021/06/11)

Photoinduced Hydroarylation and Cyclization of Alkenes with Luminescent Platinum(II) Complexes
Photoinduced hydroarylation of alkenes is an appealing synthetic strategy for arene functionalization. Herein, we demonstrated that aryl radicals generated from electron-deficient aryl chlorides/bromides could be trapped by an array of terminal/internal aryl alkenes in the presence of [Pt(O^N^C^N)] under visible-light (410 nm) irradiation, affording anti-Markovnikov hydroarylated compounds in up to 95 % yield. Besides, a protocol for [Pt(O^N^C^N)]-catalyzed intramolecular photocyclization of acrylanilides to give structurally diverse 3,4-dihydroquinolinones has been developed.
Cheng, Hanchao,Lam, Tsz-Lung,Liu, Yungen,Tang, Zhou,Che, Chi-Ming
supporting information
p. 1383 - 1389
(2020/11/30)

CO2-tuned highly selective reduction of formamides to the corresponding methylamines
We herein describe an efficient, CO2-tuned and highly selective C-O bond cleavage of N-methylated formanilides. With easy-to-handle and commercially available NaBH4 as the reductant, a variety of formanilides could be turned into the desired tertiary amines in moderate to excellent yields. The role of CO2 has been investigated in detail, and the mechanism is proposed on the basis of experiments.
Chao, Jianbin,Guo, Zhiqiang,Pang, Tengfei,Wei, Xuehong,Xi, Chanjuan,Yan, Leilei
supporting information
p. 7534 - 7538
(2021/10/12)

Borane-Trimethylamine Complex as a Reducing Agent for Selective Methylation and Formylation of Amines with CO2
We report herein that a borane-trimethylamine complex worked as an efficient reducing agent for the selective methylation and formylation of amines with 1 atm CO2 under metal-free conditions. 6-Amino-2-picoline serves as a highly efficient catalyst for the methylation of various secondary amines, whereas in its absence, the formylation of primary and secondary amines was achieved in high yield with high chemoselectivity. Mechanistic studies suggest that the 6-amino-2-picoline-borane catalytic system operates like an intramolecular frustrated Lewis pair to activate CO2.
Zhang, Yanmeng,Zhang, He,Gao, Ke
supporting information
p. 8282 - 8286
(2021/10/25)

N-Methylation of Amines with Methanol in the Presence of Carbonate Salt Catalyzed by a Metal-Ligand Bifunctional Ruthenium Catalyst [(p-cymene)Ru(2,2′-bpyO)(H2O)]
A ruthenium complex [(p-cymene)Ru(2,2′-bpyO)(H2O)] was found to be a general and efficient catalyst for the N-methylation of amines with methanol in the presence of carbonate salt. Moreover, a series of sensitive substituents, such as nitro, ester, cyano, and vinyl groups, were tolerated under present conditions. It was confirmed that OH units in the ligand are crucial for the catalytic activity. Notably, this research exhibited the potential of metal-ligand bifunctional ruthenium catalysts for the hydrogen autotransfer process.
Liu, Peng,Tung, Nguyen Thanh,Xu, Xiangchao,Yang, Jiazhi,Li, Feng
p. 2621 - 2631
(2021/02/27)

Recyclable covalent triazine framework-supported iridium catalyst for the N-methylation of amines with methanol in the presence of carbonate
An iridium complex Cp*Ir@CTF, which is synthesized by the coordinative immobilization of [Cp*IrCl2]2 on a functionalized covalent triazine framework (CTF), was found to be a general and highly efficient catalyst for the N-methylation of amines with methanol in the presence of carbonate. Under environmentally benign conditions, a variety of desirable products were obtained in high yields with complete selectivities and functional group friendliness. Furthermore, the synthesized catalyst could be recycled by simple filtration without obvious loss of catalytic activity after sixth cycle. Notably, this research exhibited the potential of covalent triazine framework-supported transition metal catalysts for hydrogen autotransfer process.
Liu, Peng,Yang, Jiazhi,Ai, Yao,Hao, Shushu,Chen, Xiaozhong,Li, Feng
p. 281 - 290
(2021/03/26)

Highly Efficient Binuclear Copper-catalyzed Oxidation of N,N-Dimethylanilines with O2
A binuclear copper-salicylate complex, [Cu(Sal)2(NCMe)]2 (Sal=salicylate), was found to be an active catalyst for the oxidation of N,N-dimethylanilines by O2, affording the corresponding N-methyl-N-phenylformamides as major products. The reactions were carried out with a O2 balloon and the S/C (substrate/catalyst ratio) of the model reaction could be up to 1×105, providing a practical and highly efficient catalytic protocol for accessing N-methyl-N-phenylformamides.
Liu, Yuxia,Yan, Yonggang,Xue, Dong,Wang, Zhongfu,Xiao, Jianliang,Wang, Chao
p. 2221 - 2225
(2020/03/23)

Transition-Metal-Free and Visible-Light-Mediated Desulfonylation and Dehalogenation Reactions: Hantzsch Ester Anion as Electron and Hydrogen Atom Donor
Novel approaches for N- and O-desulfonylation under room temperature (rt) and transition-metal-free conditions have been developed. The first methodology involves the transformation of a variety of N-sulfonyl heterocycles and phenyl benzenesulfonates to the corresponding desulfonylated products in good to excellent yields using only KOtBu in dimethyl sulfoxide (DMSO) at rt. Alternately, a visible light method has been used for deprotection of N-methyl-N-arylsulfonamides with Hantzsch ester (HE) anion serving as the visible-light-absorbing reagent and electron and hydrogen atom donor to promote the desulfonylation reaction. The HE anion can be easily prepared in situ by reaction of the corresponding HE with KOtBu in DMSO at rt. Both protocols were further explored in terms of synthetic scope as well as mechanistic aspects to rationalize key features of desulfonylation processes. Furthermore, the HE anion induces reductive dehalogenation reaction of aryl halides under visible light irradiation.
Heredia, Micaela D.,Guerra, Walter D.,Barolo, Silvia M.,Fornasier, Santiago J.,Rossi, Roberto A.,Budén, Mariá E.
supporting information
p. 13481 - 13494
(2020/12/15)

P(III)/P(V)-Catalyzed Methylamination of Arylboronic Acids and Esters: Reductive C-N Coupling with Nitromethane as a Methylamine Surrogate
The direct reductive N-arylation of nitromethane by organophosphorus-catalyzed reductive C-N coupling with arylboronic acid derivatives is reported. This method operates by the action of a small ring organophosphorus-based catalyst (1,2,2,3,4,4-hexamethylphosphetane P-oxide) together with a mild terminal reductant hydrosilane to drive the selective installation of the methylamino group to (hetero)aromatic boronic acids and esters. This method also provides for a unified synthetic approach to isotopically labeled N-methylanilines from various stable isotopologues of nitromethane (i.e., CD3NO2, CH315NO2, and 13CH3NO2), revealing this easy-to-handle compound as a versatile precursor for the direct installation of the methylamino group.
Li, Gen,Qin, Ziyang,Radosevich, Alexander T.
p. 16205 - 16210
(2020/10/26)

Reductive cyanation of organic chlorides using CO2 and NH3 via Triphos–Ni(I) species
Cyano-containing compounds constitute important pharmaceuticals, agrochemicals and organic materials. Traditional cyanation methods often rely on the use of toxic metal cyanides which have serious disposal, storage and transportation issues. Therefore, there is an increasing need to develop general and efficient catalytic methods for cyanide-free production of nitriles. Here we report the reductive cyanation of organic chlorides using CO2/NH3 as the electrophilic CN source. The use of tridentate phosphine ligand Triphos allows for the nickel-catalyzed cyanation of a broad array of aryl and aliphatic chlorides to produce the desired nitrile products in good yields, and with excellent functional group tolerance. Cheap and bench-stable urea was also shown as suitable CN source, suggesting promising application potential. Mechanistic studies imply that Triphos-Ni(I) species are responsible for the reductive C-C coupling approach involving isocyanate intermediates. This method expands the application potential of reductive cyanation in the synthesis of functionalized nitrile compounds under cyanide-free conditions, which is valuable for safe synthesis of (isotope-labeled) drugs.
Dong, Yanan,Li, Yuehui,Yang, Peiju,Zhao, Shizhen
(2020/08/19)

Selective N -monomethylation of primary anilines with the controllable installation of N -CH2D, N -CHD2, and N -CD3units
The selective N-monomethylation of primary anilines was realized by the use of the Me3N-BH3/N,N-dimethylformamide (DMF) system as the methyl source. This method also allows for the controllable introduction of N-CH2D, N-CHD2, and N-CD3 units with high lev
Meng, Jing,Wang, Yi-Feng,Wang, Zhijuan,Xia, Hui-Min,Xu, Ai-Qing,Zhang, Feng-Lian
supporting information
p. 4922 - 4926
(2020/07/30)

Bimetallic Bis-NHC-Ir(III) Complex Bearing 2-Arylbenzo[d]oxazolyl Ligand: Synthesis, Catalysis, and Bimetallic Effects
Herein, an unprecedented bimetallic bis-NHC Cp*Ir complex 1 bearing 2-arylbenzo[d]oxazolyl and NHC ligands is reported. A significant increase in activity was observed for N-methylation of amines and reduction of aldehydes with MeOH catalyzed by 1 compared to the monometallic analogues (2-11). Under the optimal conditions, it showed to be highly effective in N-methylation of nitroarenes with MeOH as both C1 and H2 source. Substrates, including aromatic amines, ketones, and nitro compounds with various functional groups, can be well-tolerated. Mechanistic studies and DFT calculation highlight the significance of bimetallic centers cooperativity.
Huang, Shuang,Hong, Xi,Cui, He-Zhen,Zhan, Bing,Li, Zhi-Ming,Hou, Xiu-Feng
p. 3514 - 3523
(2020/10/09)

Comparison of the effect of N-methyl and N-aryl groups on the hydrolytic stability and electronic properties of betalain dyes
Betalains are antioxidant secondary metabolites that emerged as safe color additives for food and cosmetics, fluorescent dyes, and redox mediators. Herein, we describe the semisynthesis of N-methyl phenylbetalain (mepBeets) and N-aryl phenylbetalain (dipBeets) dyes and compare the effect of the structure on their hydrolytic stability and electronic properties. Eight model compounds were semisynthesized by coupling betalamic acid with either N-methyl anilines or N-aryl anilines in ethyl acetate using p-toluenesulfonic acid as catalyst. The presence of electron-withdrawing substituents in the aryl moiety of mepBeets and dipBeets results in faster hydrolysis, lower anodic potentials and increased fluorescence quantum yields compared to the corresponding unsubstituted parent compounds. The results are rationalized by considering the charge distribution in the 1,7-diazaheptamethinium chromophore and are useful for the development of new hydrolytically stable betalain dyes with tunable redox and optical properties.
Bastos, Erick Leite,Dochev, Stefan,Esteves, Larissa Cerrato,Mattioli, Renan Rodini,Pioli, Renan Moraes
(2020/08/13)

Photon-initiated heterogeneous redox couples for methylation of anilines under mild conditions
Methylation of anilines has drawn a lot of attention due to their valuable applications and directly using methanol as a methylation reagent is of great advantage. Photon-initiated heterogeneous catalysis of this methylation process meets the requirements of green chemistry. Herein we show that balanced redox zones within carbon nitride supported Pd nanoparticles boost the selectivity of methylation of anilines under mild conditions.
Zhang, Bing,Gao, Hua,Wang, Wei
p. 4433 - 4437
(2020/08/10)

Catalytic and stoichiometric oxidation of N,N-dimethylanilines mediated by nonheme oxoiron(IV) complex with tetrapyridyl ligand
Nonheme iron(II) complex, [(N4Py*)FeII(CH3CN)](ClO4)2 (1) with pentadentate tetrapyridyl ligand (N4Py* = N,N-bis(2-pyridylmethyl)-1,2-di(2-pyridyl)ethylamine) has been shown to catalyze the oxidation of N,N-dimethylaniline (DMA) with H2O2, tert-butyl hydroperoxide (TBHP), peracetic acid (PAA), meta-chloroperoxybenzoic acid (mCPBA) and PhIO resulting N-methylaniline (MA) as the predominant product with N-methylformanilide (MFA) as a result of a free-radical chain process. The product composition (MA/MFA) is remarkably influenced by the electron density on the substrate, especially in the 1/mCPBA system, and by the co-oxidants used. No formation of MFA occurred when the oxidation of DMA was carried out in the presence of 1 with PhIO as co-oxidants under argon. Based on spectral investigation (UV–Vis) of reaction systems above, oxoiron(IV) intermediate, [FeIV(N4Py*)(O)]2+ (2) has been suggested to be the key active species of the N-dealkylation reaction in all catalytic systems. The shift in the λmax value of the oxoiron(IV) species in the presence of DMA from 705 to 750 nm, and the new intense absorption in the range of 5–600 nm indicates a complexation and charge-transfer (CT) type interactions between the oxidant and substrate. The stoichiometric oxidation of various N,N-dimethylaniline derivatives with 2 provided clear evidence (Hammett correlation with ρ = ?1.99, and the large negative slope (?4.1) from the logkobs versus Eoox (DMAs) plot) for the rate-determining electron transfer (ET) followed by a proton transfer (PT) process.
Lakk-Bogáth, Dóra,Kripli, Balázs,Meena, Bashdar I.,Speier, Gábor,Kaizer, József
p. 169 - 175
(2019/05/29)

Highly selective hydrogenation of amides catalysed by a molybdenum pincer complex: Scope and mechanism
A series of molybdenum pincer complexes has been shown for the first time to be active in the catalytic hydrogenation of amides. Among the tested catalysts, Mo-1a proved to be particularly well suited for the selective C-N hydrogenolysis of N-methylated formanilides. Notably, high chemoselectivity was observed in the presence of certain reducible groups including even other amides. The general catalytic performance as well as selectivity issues could be rationalized taking an anionic Mo(0) as the active species. The interplay between the amide CO reduction and the catalyst poisoning by primary amides accounts for the selective hydrogenation of N-methylated formanilides. The catalyst resting state was found to be a Mo-alkoxo complex formed by reaction with the alcohol product. This species plays two opposed roles-it facilitates the protolytic cleavage of the C-N bond but it encumbers the activation of hydrogen.
Leischner, Thomas,Artús Suarez, Lluis,Spannenberg, Anke,Junge, Kathrin,Nova, Ainara,Beller, Matthias
p. 10566 - 10576
(2019/12/02)

Dimethylanilinic N-Oxides and Their Oxygen Surrogacy Role in the Formation of a Putative High-Valent Copper-Oxygen Species
The reaction of p-cyano-N,N-dimethylaniline N-oxide, an O-atom donor, with different copper(I) complexes (at room temperature and in acetone) indicates the formation via O-atom transfer of a high-valent copper oxyl species, CuII-O?, a putative key intermediate in the catalytic cycle of copper-containing monooxygenases. The formation of p-cyano-N-hydroxymethyl-N-methylaniline and p-cyano-N-methylaniline as the main products of the reaction highlight the capability of this species to hydroxylate strong C-H bonds (bond dissociation energy ～90 kcal/mol). A plausible mechanism for the reactivity of this catalytic system is proposed.
Diaz, Daniel E.,Bhadra, Mayukh,Karlin, Kenneth D.
supporting information
p. 13746 - 13750
(2019/10/14)

N -Methylation of ortho -substituted aromatic amines with methanol catalyzed by 2-arylbenzo [d] oxazole NHC-Ir(iii) complexes
Seven new chelated cyclometalated Ir complexes of ABON,P, ABON,O, and ABON,C(carbene) based on a rigid and tunable 2-arylbenzo[d]oxazole backbone have been prepared for the N-methylation of amines. Among these three coordinated modes, ABON,C(carbene)-chelated iridium-based catalysts exhibited good performance in the monomethylation of aromatic amines with methanol (MeOH) as the green methylation reagent. The steric-modified synthesis of ABON,C(carbene) complexes was described. The most active ABON,C(carbene) complex with marginal steric hindrance as a catalyst was obtained from the benzoxazole ring without a substituent and methyl group of the benzimidazole ring on the N-heterocyclic carbene (NHC) ligand. A variety of amines including para- and meta-substituted aromatic amines, as well as heterocyclic amines, were formulated as suitable substrates. Importantly, this catalyst considerably promoted the yield of the N-methylation of ortho-substituted aromatic amines. Controlled kinetic experiments and deuterium-labeling reactions of these ortho-substituted amines were conducted under optimized conditions. On the basis of the experimental results, a plausible mechanism was proposed.
Huang, Shuang,Hong, Xi,Cui, He-Zhen,Zhou, Quan,Lin, Yue-Jian,Hou, Xiu-Feng
p. 5072 - 5082
(2019/04/17)

Iron-Catalyzed Regioselective α-C-H Alkylation of N-Methylanilines: Cross-Dehydrogenative Coupling between Unactivated C(sp3)-H and C(sp3)-H Bonds via a Radical Process
The iron-catalyzed α-C-H alkylation of N-methylanilines without any directing group by cross-dehydrogenative coupling between unactivated C(sp3)-H and C(sp3)-H bonds has been established for the first time, which provides a good complement to C(sp3)-H activation reactions and expands the field of Fe-catalyzed C-H functionalizations. Many different C(sp3)-H bonds in cyclic alkanes, cyclic ethers, and toluene derivatives can be used as coupling partners. Mechanistic investigations including the radical reaction process, the main role of various reagents, and the kinetic isotope effect experiment were also described.
Li, Ze-Lin,Sun, Kang-Kang,Wu, Peng-Yu,Cai, Chun
p. 6830 - 6839
(2019/06/14)

Photoinduced Cross-Coupling of Amines with 1,2-Diiodobenzene and Its Application in the Synthesis of Carbazoles
A facile and efficient process for the preparation of various tertiary aminobenzenes and carbazole derivatives via photoinduced cross-coupling of amines with 1,2-diiodobenzene is reported. Mechanistic investigations indicate that the transformation proceeds via nucleo-philic addition of an amine to the benzyne intermediate accompanied with a proton transfer process, followed by an oxidative cyclization of the generated diphenylamine to furnish the corresponding carbazole products.
Zhao, Xinxin,Chen, Ming,Huang, Binbin,Yang, Chao,Gao, Yuan,Xia, Wujiong
supporting information
p. 2981 - 2989
(2018/05/15)

Evaluation of 4-phenylamino-substituted naphthalene-1,2-diones as tubulin polymerization inhibitors
A series of 4-phenylamino-substituted naphthalene-1,2-dione derivatives were prepared and evaluated as effective antiproliferative agents. MTT assays showed that the compounds with a methyl group on the nitrogen linker exhibited potent antiproliferative activities against human cancer cells. The mechanistic study revealed that these compounds could induce mitochondrial depolarization, which resulted in intracellular ROS production, and they also acted as tubulin polymerization inhibitors. Moreover, the typical compound could arrest A549 cells in the G2/M phase, resulting in cellular apoptosis and induced mitotic arrest in A549 cells through disrupting microtubule dynamics.
Yang, Honghao,An, Baijiao,Li, Xingshu,Zeng, Wei
p. 3057 - 3063
(2018/08/09)

Methylation of Amines and Ketones with Methanol Catalyzed by an Iridium Complex Bearing a 2-Hydroxypyridylmethylene Fragment
Reaction of complex [Cp?Ir(HOC5H3CH2C5H3OH)Cl][Cl] (1) with AgOTf generated the product [Cp?Ir(HOC5H3CH2C5H3OH)(H2O)][OTf]2 (2), which was further transformed to the complex [Cp?Ir(OC5H3CH2C5H3O)(H2O)] (3) in the presence of t-BuONa via -OH deprotonation. Complexes 1-3 exhibited high activity for the methylation of amines and ketones. These C-C and C-N coupling reactions proceeded in air with 1 mol % catalyst loading in the presence of K2CO3.
Deng, Danfeng,Hu, Bowen,Yang, Min,Chen, Dafa
p. 3353 - 3359
(2018/09/25)

Efficient and versatile catalytic systems for the n-methylation of primary amines with methanol catalyzed by n-heterocyclic carbene complexes of iridium
Efficient and versatile catalytic systems were developed for the N-methylation of both aliphatic and aromatic primary amines using methanol as the methylating agent. Iridium complexes bearing an Nheterocyclic carbene (NHC) ligand exhibited high catalytic performance for this type of transformation. For aliphatic amines, selective N,N-dimethylation was achieved at low temperatures (50-90 °C). For aromatic amines, selective N-monomethylation and selective N,N-dimethylation were accomplished by simply changing the reaction conditions (presence or absence of a base with an appropriate catalyst). These findings can be used to develop methods for synthesizing useful amine compounds having N-methyl or N,N-dimethyl moieties.
Toyooka, Genki,Tuji, Akiko,Fujita, Ken-Ichi
p. 4617 - 4626
(2019/02/01)

Well-Defined Phosphine-Free Iron-Catalyzed N-Ethylation and N-Methylation of Amines with Ethanol and Methanol
An iron(0) complex bearing a cyclopentadienone ligand catalyzed N-methylation and N-ethylation of aryl and aliphatic amines with methanol or ethanol in mild and basic conditions through a hydrogen autotransfer borrowing process is reported. A broad range of aromatic and aliphatic amines underwent mono- or dimethylation in high yields. DFT calculations suggest molecular hydrogen acts not only as a reducing agent but also as an additive to displace thermodynamic equilibria.
Lator, Alexis,Gaillard, Sylvain,Poater, Albert,Renaud, Jean-Luc
supporting information
p. 5985 - 5990
(2018/10/02)

N-Monomethylation of Aromatic Amines with Methanol via PNHP-Pincer Ru Catalysts
The use of methanol for the selective methylation of aromatic amines with RuHCl(CO)(PNHP) (PNHP = bis(2-diphenylphosphinoethyl)amine) is reported. Various aromatic amines were transformed into their corresponding monomethylated secondary amines in high yields at 150 °C with a very low catalyst loading (0.02-0.1 mol %) in the presence of KOtBu (20-60 mol %). The catalyst precursor, RuHCl(CO)(PNHP), was converted to [RuH(CO)2(PNHP)]+ under the catalytic conditions and also serves as a highly effective catalyst. The robustness of this catalyst contributes to its outstanding catalytic activity, even under reaction conditions, in which CO is liberated from methanol.
Ogata, Osamu,Nara, Hideki,Fujiwhara, Mitsuhiko,Matsumura, Kazuhiko,Kayaki, Yoshihito
supporting information
p. 3866 - 3870
(2018/07/25)

Expedient stereospecific Co-catalyzed tandem C-N and C-O bond formation of: N -methylanilines with styrene oxides
Cobalt(ii)-catalyzed stereospecific coupling of N-methylanilines with styrene oxides is developed via tandem C-N and C-O bond formation using tert-butyl hydroperoxide (TBHP) as an oxidant. Optically active epoxide can be reacted with high optical purity.
Satheesh, Vanaparthi,Vivek Kumar, Sundaravel,Punniyamurthy, Tharmalingam
supporting information
p. 11813 - 11816
(2018/12/01)

Method for selectively preparing N-monomethylamine compound
The invention discloses a method for selectively preparing an N-monomethylamine compound. The method takes an amine compound, formaldehyde and H2 as reaction raw materials; the raw materials react in a reaction medium in the presence of a compound catalyst at 30 DEG C-180 DEG C for 2h-48h, so as to obtain the N-monomethylamine compound; and the compound catalyst is composed of oxides of at least two of the following metal or oxides of least one of the following metal and at least one metal simple substance: aluminum, copper, nickel, cobalt and iron. According to the method for preparing the N-monomethylamine compound, the conversion ratio and the selectivity of N-monomethylamine are relatively high; the H2 is used as a reducing agent and is clean, cheap and environment-friendly; the catalyst utilized by the method is cheap, simple to prepare and high in catalysis efficiency; and the method has mild preparation and reaction conditions and the catalyst has no corrosiveness, is easy to separate and can be repeatedly used.
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Paragraph 0032-0033

(2017/08/29)

Nickel-Catalyzed C-CN Bond Formation via Decarbonylative Cyanation of Esters, Amides, and Intramolecular Recombination Fragment Coupling of Acyl Cyanides
An efficient nickel-catalyzed decarbonylative cyanation reaction which allows the direct functional-group interconversion of readily available esters into the corresponding nitriles was developed. This reaction successfully offers access to structurally diverse nitriles with high efficiency and excellent functional-group tolerance and provides a good alternative to classical synthetic pathways from diazonium salts or organic halide compounds.
Chatupheeraphat, Adisak,Liao, Hsuan-Hung,Lee, Shao-Chi,Rueping, Magnus
supporting information
p. 4255 - 4258
(2017/08/23)

N -Monomethylation of amines using paraformaldehyde and H2
The selective N-monomethylation of amines is an important topic in fine chemical synthesis. Herein, for the first time, we described a selective N-monomethylation reaction of amines with paraformaldehyde and H2 in the presence of a CuAlOx catalyst. A variety of amines, including primary aromatic amines, benzylamine and cyclohexylamine, as well as secondary amines, have been shown to be compatible with this reaction.
Wang, Hongli,Huang, Yongji,Dai, Xingchao,Shi, Feng
supporting information
p. 5542 - 5545
(2017/07/06)

Efficient Cobalt-Catalyzed Methylation of Amines Using Methanol
The methylation of amines using methanol is a promising route to synthesize N-methylamines, and the development of cheap and efficient catalytic system for this reaction is of great significance. Herein, we reported a cobalt (Co)-based catalytic system, which was in situ formed from commercially available Co precursor and a tetradentate phosphine ligand P(CH2CH2PPh2)3 combined with K3PO4. This catalystic system was very effective for the selective production of dimethylated products from aliphatic amines and monomethylated ones from aromatic amines. The reaction mechanism was further investigated by control and isotope labelling experiments. (Figure presented.).
Liu, Zhenghui,Yang, Zhenzhen,Yu, Xiaoxiao,Zhang, Hongye,Yu, Bo,Zhao, Yanfei,Liu, Zhimin
supporting information
p. 4278 - 4283
(2017/10/23)

N-Methylation of Amines with Methanol Catalyzed by a Cp?Ir Complex Bearing a Functional 2,2′-Bibenzimidazole Ligand
A new type of Cp?Ir complex bearing a functional 2,2′-bibenzimidazole ligand was designed, synthesized, and found to be a highly effective and general catalyst for the N-methylation of a variety of amines with methanol in the presence of a weak base (0.3 equiv of Cs2CO3).
Liang, Ran,Li, Shun,Wang, Rongzhou,Lu, Lei,Li, Feng
supporting information
p. 5790 - 5793
(2017/11/10)

Mono-N-methylation of anilines with methanol catalyzed by a manganese pincer-complex
The selective mono-N-methylation of anilines derivatives was achieved under mild conditions using inexpensive methanol as C1 source. Under hydrogen borrowing conditions, using a tridentate PN3P manganese pre-catalyst (5?mol%), a catalytic amount of base (20?mol%), for 24?h at 120?°C, a large variety of anilines derivatives was methylated in good to excellent yield. Mechanistic investigations allowed us to isolate and characterize by X-ray diffraction studies a de-aromatized manganese intermediate.
Bruneau-Voisine, Antoine,Wang, Ding,Dorcet, Vincent,Roisnel, Thierry,Darcel, Christophe,Sortais, Jean-Baptiste
p. 57 - 62
(2017/02/13)

Stereospecific copper-catalyzed domino ring opening and sp3 C-H functionalization of activated aziridines with N-alkylanilines
Copper efficiently catalyzed nucleophilic ring opening, sp3 C-H functionalization, and C-N bond formation in the presence of tert-butyl hydroperoxide to afford functionalized imidazolidines starting from N-sulfonylaziridines and Nalkylanilines. The products were obtained in high optical purities (95 → 99% ee) with excellent functional group tolerance.
Sengoden, Mani,Bhowmick, Abhisikta,Punniyamurthy, Tharmalingam
supporting information
p. 158 - 161
(2017/11/27)

Bimetallic nanosized solids with acid and redox properties for catalytic activation of C-C and C-H bonds
A new approach is presented to form self-supported bimetallic nanosized solids with acid and redox catalytic properties. They are water-, air- and H2-stable, and are able to activate demanding C-C and C-H reactions. A detailed mechanistic study on the formation of the Ag-Fe bimetallic system shows that a rapid redox-coupled sequence between Ag+, O2 (air) and Fe2+ occurs, giving monodisperse Ag nanoparticles supported by O-bridged diatomic Fe3+ triflimides. The system can be expanded to Ag nanoparticles embedded within a matrix of Cu2+, Bi3+ and Yb3+ triflimide.
Cabrero-Antonino, Jose R.,Tejeda-Serrano, María,Quesada, Manuel,Vidal-Moya, Jose A.,Leyva-Pérez, Antonio,Corma, Avelino
p. 689 - 696
(2016/12/28)

N-Methylation of poorly nucleophilic aromatic amines with dimethyl carbonate
Abstract: Dimethyl carbonate (DMC), an environmentally friendly methylation agent, is a substitute for traditional methylation agents such as methyl halides (CH3X, X?=?I, Br, Cl) or dimethyl sulfate. An efficient, convenient, and green method has been developed for N-methylation of poorly nucleophilic aromatic amines with DMC. It was found that the couple PEG400/K2CO3 provides good selectivity for the N-methylation product. Finally, the mechanism for reaction of amines with DMC was investigated, and a plausible multistep mechanism proposed and verified. Graphical Abstract: [Figure not available: see fulltext.]
Yan, Huidong,Zeng, Liufang,Xie, Yaqiang,Cui, Yu,Ye, Liyi,Tu, Song
p. 5951 - 5960
(2016/06/01)

Isotope effect profiles in the N-demethylation of N,N-dimethylanilines: A key to determine the pKa of nonheme Fe(III)-OH complexes
N-demethylation of N,N-dimethylanilines promoted by [(N4Py)FeIVO]2+ occurs by an electron transfer-proton transfer (ET-PT) mechanism with a rate determining PT step. From the bell-shaped curve of the KDIE profile it has been estimated that the pKa of [(N4Py)FeIII-OH]2+ is 9.7.
Barbieri, Alessia,De Gennaro, Martina,Di Stefano, Stefano,Lanzalunga, Osvaldo,Lapi, Andrea,Mazzonna, Marco,Olivo, Giorgio,Ticconi, Barbara
p. 5032 - 5035
(2015/03/30)

Redox inactive metal ion triggered N-dealkylation by an iron catalyst with dioxygen activation: A lesson from lipoxygenases
Utilization of dioxygen as the terminal oxidant at ambient temperature is always a challenge in redox chemistry, because it is hard to oxidize a stable redox metal ion like iron(iii) to its high oxidation state to initialize the catalytic cycle. Inspired by the dioxygenation and co-oxidase activity of lipoxygenases, herein, we introduce an alternative protocol to activate the sluggish iron(iii) species with non-redox metal ions, which can promote its oxidizing power to facilitate substrate oxidation with dioxygen, thus initializing the catalytic cycle. In oxidations of N,N-dimethylaniline and its analogues, adding Zn(OTf)2 to the [Fe(TPA)Cl2]Cl catalyst can trigger the amine oxidation with dioxygen, whereas [Fe(TPA)Cl2]Cl alone is very sluggish. In stoichiometric oxidations, it has also been confirmed that the presence of Zn(OTf)2 can apparently improve the electron transfer capability of the [Fe(TPA)Cl2]Cl complex. Experiments using different types of substrates as trapping reagents disclosed that the iron(iv) species does not occur in the catalytic cycle, suggesting that oxidation of amines is initialized by electron transfer rather than hydrogen abstraction. Combined experiments from UV-Vis, high resolution mass spectrometry, electrochemistry, EPR and oxidation kinetics support that the improved electron transfer ability of iron(iii) species originates from its interaction with added Lewis acids like Zn2+ through a plausible chloride or OTf- bridge, which has promoted the redox potential of iron(iii) species. The amine oxidation mechanism was also discussed based on the available data, which resembles the co-oxidase activity of lipoxygenases in oxidative dealkylation of xenobiotic metabolisms where an external electron donor is not essential for dioxygen activation.
Zhang, Jisheng,Wang, Yujuan,Luo, Nengchao,Chen, Zhuqi,Wu, Kangbing,Yin, Guochuan
p. 9847 - 9859
(2015/06/08)

Efficient ruthenium-catalyzed N-methylation of amines using methanol
An in situ-generated complex from [RuCpCl2]2 and dpePhos ligand is reported as an efficient catalyst in the presence of 5 mol % of LiOtBu for the N-methylation of amines using methanol as the methylating agent at moderate conditions, following hydrogen borrowing strategy. This simple catalyst system provides selective N-monomethylation of substituted primary anilines and sulfonamides as well as N,N dimethylation of primary aliphatic amines in excellent yields at 40-100 °C with good tolerance to reducible functional groups. The catalytic intermediate CpRu(dpePhos)H was isolated and was shown to be active for methylation in the absence of base.
Dang, Tuan Thanh,Ramalingam, Balamurugan,Seayad, Abdul Majeed
p. 4082 - 4088
(2015/11/11)

Nickel-catalyzed amination of Aryl chlorides with ammonia or ammonium salts
The nickel-catalyzed amination of aryl chlorides to form primary arylamines occurs with ammonia or ammonium sulfate and a well-defined single-component nickel(0) precatalyst containing a Josiphos ligand and an η2-bound benzonitrile ligand. This system also catalyzes the coupling of aryl chlorides with gaseous amines in the form of their hydrochloride salts. Simple alternative: The title reaction, which results in primary arylamines, is catalyzed by well-defined single-component nickel(0) precatalysts containing a Josiphos ligand and an η2-bound benzonitrile ligand. This system also catalyzes the coupling of aryl chlorides with gaseous amines in the form of their hydrochloride salts.
Green, Rebecca A.,Hartwig, John F.
supporting information
p. 3768 - 3772
(2015/03/18)

Direct condensation of functionalized sp3 carbons with formanilides for enamine synthesis using an in situ generated HMDS amide catalyst
The efficient synthesis of functionalized enamines including β-enaminoesters was effectively accomplished by the direct condensation of functionalized sp3 carbanions such as acetates with formamides using in situ generated HMDS base from catalytic cesium fluoride and stoichiometric tristrimethylsilylamine. This journal is the Partner Organisations 2014.
Taneda, Hiroshi,Inamoto, Kiyofumi,Kondo, Yoshinori
supporting information
p. 6523 - 6525
(2014/06/09)

A general method for N-methylation of amines and nitro compounds with dimethylsulfoxide
DMSO methylates a broad range of amines in the presence of formic acid, providing a novel, green and practical method for amine methylation. The protocol also allows the one-pot transformation of aromatic nitro compounds into dimethylated amines in the presence of a simple iron catalyst. Not just a solvent: DMSO methylates a broad range of amines in the presence of formic acid, providing a novel, green and practical method for amine methylation. The protocol also allows the one-pot transformation of aromatic nitro compounds into dimethylated amines in the presence of a simple iron catalyst. Copyright
Jiang, Xue,Wang, Chao,Wei, Yawen,Xue, Dong,Liu, Zhaotie,Xiao, Jianliang
supporting information
p. 58 - 63
(2014/01/17)

Scandium ion-enhanced oxidative dimerization and N -demethylation of N, N -dimethylanilines by a non-heme iron(IV)-oxo complex
Oxidative dimerization of N,N-dimethylaniline (DMA) occurs with a nonheme iron(IV)-oxo complex, [FeIV(O)(N4Py)]2+ (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine), to yield the corresponding dimer, tetramethylbenzidine (TMB), in acetonitrile. The rate of the oxidative dimerization of DMA by [FeIV(O)(N4Py)]2+ is markedly enhanced by the presence of scandium triflate, Sc(OTf)3 (OTf = CF3SO3-), when TMB is further oxidized to the radical cation (TMB?+). In contrast, we have observed the oxidative N-demethylation with para-substituted DMA substrates, since the position of the C-C bond formation to yield the dimer is blocked. The rate of the oxidative N-demethylation of para-substituted DMA by [FeIV(O) (N4Py)]2+ is also markedly enhanced by the presence of Sc(OTf) 3. In the case of para-substituted DMA derivatives with electron-donating substituents, radical cations of DMA derivatives are initially formed by Sc3+ ion-coupled electron transfer from DMA derivatives to [FeIV(O)(N4Py)]2+, giving demethylated products. Binding of Sc3+ to [FeIV(O)(N4Py)]2+ enhances the Sc3+ ion-coupled electron transfer from DMA derivatives to [Fe IV(O)(N4Py)]2+, whereas binding of Sc3+ to DMA derivatives retards the electron-transfer reaction. The complicated kinetics of the Sc3+ ion-coupled electron transfer from DMA derivatives to [FeIV(O)(N4Py)]2+ are analyzed by competition between binding of Sc3+ to DMA derivatives and to [FeIV(O)(N4Py)] 2+. The binding constants of Sc3+ to DMA derivatives increase with the increase of the electron-donating ability of the para-substituent. The rate constants of Sc3+ ion-coupled electron transfer from DMA derivatives to [FeIV(O)(N4Py)]2+, which are estimated from the binding constants of Sc3+ to DMA derivatives, agree well with those predicted from the driving force dependence of the rate constants of Sc3+ ion-coupled electron transfer from one-electron reductants to [FeIV(O)(N4Py)]2+. Thus, oxidative dimerization of DMA and N-demethylation of para-substituted DMA derivatives proceed via Sc3+ ion-coupled electron transfer from DMA derivatives to [FeIV(O)(N4Py)]2+.
Park, Jiyun,Morimoto, Yuma,Lee, Yong-Min,You, Youngmin,Nam, Wonwoo,Fukuzumi, Shunichi
experimental part
p. 11612 - 11622
(2012/01/12)

A facile and practical copper powder-catalyzed, organic solvent-and ligand-free ullmann amination of aryl halides
A facile and practical method that the copper powder-catalyzed Ullmann amination of aryl halides with aqueous methylamine under organic solvent-and ligand-free condition at 100 °C and in air gave N-arylamines as sole products in good to excellent yields. The presence of a small amount of air is essential. Other aliphatic primary amines show good to very high reactivity. Secondary amines and aniline are not reactive. Sensitive substituents (i.e., CHO, MeCO, CN and Cl) are tolerable in the reaction.
Jiao, Jiao,Zhang, Xi-Ru,Chang, Ning-Hui,Wang, Jie,Wei, Jun-Fa,Shi, Xian-Ying,Chen, Zhan-Guo
supporting information; experimental part
p. 1180 - 1183
(2011/04/24)

N-Demethylation of N,N-Dimethylanilines by the benzotriazole N-Oxyl radical: Evidence for a two-step electron transfer-proton transfer mechanism
"Chemical Equation Presented" The reaction of the benzotriazole N-oxyl radical (BTNO) with a series of 4-X-N,N-dimethylanilines (X = CN, CF 3, CO2CH2CH3, CH3, OC6H5, OCH3) has been investigated in CH 3CN. Product analysis shows that the radical, 4-X-C6H 4N(CH3)CH2·, is first formed, which can lead to the N-demethylated product or the product of coupling with BTNO. Reaction rates were found to increase significantly by increasing the electron-donating power of the aryl substituents (p+ = -3.8). With electron-donating substituents (X = CH3, OC6H5, OCH3), no intermolecular deuterium kinetic isotope effect (DKIE) and a substantial intramolecular DKIE are observed. With electron-withdrawing substituents (X = CN, CF3, CO2CH2CH 3), substantial values of both intermolecular and intramolecular DKIEs are observed. These results can be interpreted on the basis of an electron-transfer mechanism from the N,N-dimethylanilines to the BTNO radical followed by deprotonation of the anilinium radical cation (ET-PT mechanism). By applying the Marcus equation to the kinetic data for X = CH3, OC 6H5, OCH3 (rate-determining ET), a reorganization energy for the ET reaction was determined (λ BTNO/DMA= 32.1 kcal mol- 1). From the self-exchange reorganization energy for the BTNO/BTNO- couple, a self-exchange reorganization energy value of 31.9 kcal mol-1 was calculated for the DMA·+/DMA couple.
Baciocchi, Enrico,Bietti, Massimo,Lanzalunga, Osvaldo,Lapi, Andrea,Raponi, Daniele
experimental part
p. 1378 - 1385
(2010/06/11)

Anilinic N-oxides support cytochrome P450-mediated N-dealkylation through hydrogen-atom transfer
The mechanism of N-dealkylation mediated by cytochrome P450 (P450) has long been studied and argued as either a single electron transfer (SET) or a hydrogen atom transfer (HAT) from the amine to the oxidant of the P450, the reputed iron-oxene. In our study, tertiary anilinic N-oxides were used as oxygen surrogates to directly generate a P450-mediated oxidant that is capable of N-dealkylating the dimethylaniline derived from oxygen donation. These surrogates were employed to probe the generated reactive oxygen species and the subsequent mechanism of N-dealkylation to distinguish between the HAT and SET mechanisms. In addition to the expected N-demethylation of the product aniline, 2,3,4,5,6-pentafluoro-N,N-dimethylaniline N-oxide (PFDMAO) was found to be capable of N-dealkylating both N,N-dimethylaniline (DMA) and N-cyclopropyl-N-methylaniline (CPMA). Rate comparisons of the N-demethylation of DMA supported by PFDMAO show a 27-fold faster rate than when supported by N,N-dimethylaniline N-oxide (DMAO). Whereas intermolecular kinetic isotope effects were masked, intramolecular measurements showed values reflective of those seen previously in DMAO- and the native NADPH/O2-supported systems (2.33 and 2.8 for the N-demethylation of PFDMA and DMA from the PFDMAO system, respectively). PFDMAO-supported N-dealkylation of CPMA led to the ring-intact product N-cyclopropylaniline (CPA), similar to that seen with the native system. The formation of CPA argues against a SET mechanism in favor of a P450-like HAT mechanism. We suggest that the similarity of KIEs, in addition to the formation of the ring-intact CPA, argues for a similar mechanism of Compound I (Cpd I) formation followed by HAT for N-dealkylation by the native and N-oxide-supported systems and demonstrate the ability of the N-oxide-generated oxidant to act as an accurate mimic of the native P450 oxidant.
Roberts, Kenneth M.,Jones, Jeffery P.
experimental part
p. 8096 - 8107
(2010/09/11)

A facile protocol for the synthesis of mono-N-methyl anilines via formimidate intermediates
A general procedure for the preparation of mono-N-methyl anilines has been developed with excellent yields. This protocol relies on a NaBH3(OAc) reduction of formimidate intermediates that are quantitatively generated by treatment of primary substituted anilines with triethyl orthoformate under the catalysis of MCM-41-SO3H mesoporous zeolite. The newly developed procedure was facile, efficient, and environmentally benign.
Sun, Nan,Wang, Shuai,Mo, Weimin,Hu, Baoxiang,Shen, Zhenlu,Hu, Xinquan
experimental part
p. 7142 - 7148
(2010/09/14)

Radioprotectors
A compound of the formula (Ib): wherein X is NCH3, Y is N, Z is N, R3 is N(CH3)2, and (a) R1 is CH3, R2, R4 and R5 to R11 are hydrogen or (b) R5 is CH3 and R1, R2, R4 and R6 to R11 are hydrogen, and salts and tautomers thereof.
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(2009/04/23)

2-ARYL- AND 2-HETEROARYLTHIAZOLYL COMPOUNDS, METHODS FOR THEIR PREPARATION AND USE THEREOF
The present invention discloses fused bicyclic 2-aryl- or 2-heteroarylthiazolyl compounds and their pharmaceutically acceptable salts and esters thereof, which are useful for inhibiting the growth of cancerous cells, inhibiting human breast carcinoma tumo
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(2009/10/22)