- Additive-freeN-methylation of amines with methanol over supported iridium catalyst
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An efficient and versatile zinc oxide-supported iridium (Ir/ZnO) catalyst was developed to catalyze the additive-freeN-methylation of amines with methanol. Mechanistic studies suggested that the high catalytic reactivity is rooted in the small sizes (1.4 nm) of Ir nanoparticles and the high ratio (93%) of oxidized iridium species (IrOx, Ir3+and Ir4+) on the catalyst. Moreover, the delicate cooperation between the IrOxand ZnO support also promoted its high reactivity. The selectivity of this catalyticN-methylation was controllable between dimethylation and monomethylation by carefully tuning the catalyst loading and reaction solvent. Specifically, neat methanol with high catalyst loading (2 mol% Ir) favored the formation ofN,N-dimethylated amine, while the mesitylene/methanol mixture with low catalyst loading (0.5 mol% Ir) was prone to producing mono-N-methylated amines. An environmentally benign continuous flow system with a recycled mode was also developed for the efficient production ofN-methylated amines. With optimal flow rates and amine concentrations, a variety ofN-methylamines were produced with good to excellent yields in this Ir/ZnO-based flow system, providing a starting point for the clean and efficient production ofN-methylamines with this cost-effective chemical process.
- Liu, Xiang,Loh, Teck-Peng,Qiang, Wenwen,Wang, Jing,Ye, Sen,Zhu, Longfei
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p. 3364 - 3375
(2021/06/06)
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- Trialkylammonium salt degradation: Implications for methylation and cross-coupling
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Trialkylammonium (most notably N,N,N-trimethylanilinium) salts are known to display dual reactivity through both the aryl group and the N-methyl groups. These salts have thus been widely applied in cross-coupling, aryl etherification, fluorine radiolabelling, phase-transfer catalysis, supramolecular recognition, polymer design, and (more recently) methylation. However, their application as electrophilic methylating reagents remains somewhat underexplored, and an understanding of their arylation versus methylation reactivities is lacking. This study presents a mechanistic degradation analysis of N,N,N-trimethylanilinium salts and highlights the implications for synthetic applications of this important class of salts. Kinetic degradation studies, in both solid and solution phases, have delivered insights into the physical and chemical parameters affecting anilinium salt stability. 1H NMR kinetic analysis of salt degradation has evidenced thermal degradation to methyl iodide and the parent aniline, consistent with a closed-shell SN2-centred degradative pathway, and methyl iodide being the key reactive species in applied methylation procedures. Furthermore, the effect of halide and non-nucleophilic counterions on salt degradation has been investigated, along with deuterium isotope and solvent effects. New mechanistic insights have enabled the investigation of the use of trimethylanilinium salts in O-methylation and in improved cross-coupling strategies. Finally, detailed computational studies have helped highlight limitations in the current state-of-the-art of solvation modelling of reaction in which the bulk medium undergoes experimentally observable changes over the reaction timecourse. This journal is
- Assante, Michele,Baillie, Sharon E.,Juba, Vanessa,Leach, Andrew G.,McKinney, David,Reid, Marc,Washington, Jack B.,Yan, Chunhui
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p. 6949 - 6963
(2021/06/02)
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- Compound used as blue pressure-sensitive dye and preparation method and application thereof
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The invention relates to a compound used as a blue pressure-sensitive dye, and the structural general formula of the compound is shown in the specification, in the formula, R1 is CH3, CH2CH3, CH2CH2CH3 or CH2CH2CH2CH3; and R2 is CH3 or CH2CH3. Three key intermediates including substituted indole, reactive hydrogen substituted m-aminophenol and chlorophthalic anhydride are adopted, and the target compound used as the blue pressure-sensitive dye is obtained through two-step condensation. Raw materials required for synthesis are easy to obtain, the conversion rate of each step in the synthesis process is high, and no complex purification procedure is needed in the intermediate process. The target compound is high in color rendering property, the molar absorption coefficient of the target compound reaches 1.8 times that of CVL, and the same color rendering effect of CVL can be achieved under the low pressure-sensitive dye using concentration.
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Paragraph 0020; 0021
(2021/02/06)
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- Metal-Free Deoxygenation of Amine N-Oxides: Synthetic and Mechanistic Studies
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We report herein an unprecedented combination of light and P(III)/P(V) redox cycling for the efficient deoxygenation of aromatic amine N-oxides. Moreover, we discovered that a large variety of aliphatic amine N-oxides can easily be deoxygenated by using only phenylsilane. These practically simple approaches proceed well under metal-free conditions, tolerate many functionalities and are highly chemoselective. Combined experimental and computational studies enabled a deep understanding of factors controlling the reactivity of both aromatic and aliphatic amine N-oxides.
- Lecroq, William,Schleinitz, Jules,Billoue, Mallaury,Perfetto, Anna,Gaumont, Annie-Claude,Lalevée, Jacques,Ciofini, Ilaria,Grimaud, Laurence,Lakhdar, Sami
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p. 1237 - 1242
(2021/06/01)
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- Anchimerically Assisted Selective Cleavage of Acid-Labile Aryl Alkyl Ethers by Aluminum Triiodide and N, N-Dimethylformamide Dimethyl Acetal
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Aluminum triiodide is harnessed by N,N-dimethylformamide dimethyl acetal (DMF-DMA) for the selective cleavage of ethers via neighboring group participation. Various acid-labile functional groups, including carboxylate, allyl, tert-butyldimethylsilyl (TBS), and tert-butoxycarbonyl (Boc), suffer the conditions intact. The method offers an efficient approach to cleaving catechol monoalkyl ethers and to uncovering phenols from acetal-type protecting groups such as methoxymethyl (MOM), methoxyethoxymethyl (MEM), and tetrahydropyranyl (THP) chemoselectively.
- Sang, Dayong,Yue, Huaxin,Zhao, Zhengdong,Yang, Pengtao,Tian, Juan
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p. 6429 - 6440
(2020/07/14)
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- Para-Selective C-H Olefination of Aniline Derivatives via Pd/S,O-Ligand Catalysis
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Herein we report a highly para-selective C-H olefination of aniline derivatives by a Pd/S,O-ligand-based catalyst. The reaction proceeds under mild reaction conditions with high efficiency and broad substrate scope, including mono-, di-, and trisubstituted tertiary, secondary, and primary anilines. The S,O-ligand is responsible for the dramatic improvements in substrate scope and the high para-selectivity observed. This methodology is operationally simple, scalable, and can be performed under aerobic conditions.
- Naksomboon, Kananat,Poater, Jordi,Bickelhaupt, F. Matthias,Fernández-Ibá?ez, M. ángeles
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supporting information
p. 6719 - 6725
(2019/05/06)
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- Benzo polyaza and phosphole oxygen ligand and complex containing same, preparation method and application
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The invention discloses a benzo polyaza and phosphole oxygen ligand and a complex containing same, a preparation method and application. The invention provides a benzo polyaza and phosphole oxygen ligand as shown in formula I and a complex containing same. A complex of the benzo polyaza and phosphole oxygen ligand and a transition metal halide enables direct coupling of carbon-carbon bonds betweenbig steric hindrance alkyl and aryl; the reaction conditions are gentle; the catalyzing efficiency is high; the coupling reaction process of the carbon-carbon bonds between big steric hindrance alkyland aryl can be extremely simplified; the practicability is high; the reaction cost can be obviously decreased, and the reaction period is reduced; the complex is free from other side products without being required in the catalyzing process. The formula refers to the description.
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Paragraph 0134; 0135; 0136; 0137; 0138
(2019/01/16)
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- Synthesis of Halogenated Anilines by Treatment of N, N-Dialkylaniline N-Oxides with Thionyl Halides
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The special reactivity of N,N-dialkylaniline N-oxides allows practical and convenient access to electron-rich aryl halides. A complementary pair of reaction protocols allow for the selective para-bromination or ortho-chlorination of N,N-dialkylanilines in up to 69% isolated yield. The generation of a diverse array of halogenated anilines is made possible by a temporary oxidation level increase of N,N-dialkylanilines to the corresponding N,N-dialkylaniline N-oxides and the excision of the resultant weak N-O bond via treatment with thionyl bromide or thionyl chloride at low temperature.
- Reed, Hayley,Paul, Tyler R.,Chain, William J.
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p. 11359 - 11368
(2018/08/06)
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- Efficient and Selective N-Methylation of Nitroarenes under Mild Reaction Conditions
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Herein, we report a straightforward protocol for the preparation of N,N-dimethylated amines from readily available nitro starting materials using formic acid as a renewable C1 source and silanes as reducing agents. This tandem process is efficiently accomplished in the presence of a cubane-type Mo3PtS4 catalyst. For the preparation of the novel [Mo3Pt(PPh3)S4Cl3(dmen)3]+ (3+) (dmen: N,N′-dimethylethylenediamine) compound we have followed a [3+1] building block strategy starting from the trinuclear [Mo3S4Cl3(dmen)3]+ (1+) and Pt(PPh3)4 (2) complexes. The heterobimetallic 3+ cation preserves the main structural features of its 1+ cluster precursor. Interestingly, this catalytic protocol operates at room temperature with high chemoselectivity when the 3+ catalyst co-exists with its trinuclear 1+ precursor. N-heterocyclic arenes, double bonds, ketones, cyanides and ester functional groups are well retained after N-methylation of the corresponding functionalized nitroarenes. In addition, benzylic-type as well as aliphatic nitro compounds can also be methylated following this protocol.
- Pedrajas, Elena,Sorribes, Iván,Guillamón, Eva,Junge, Kathrin,Beller, Matthias,Llusar, Rosa
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p. 13205 - 13212
(2017/09/12)
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- Base-oxidant promoted metal-free N-demethylation of arylamines
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A metal-free oxidative N-demethylation of arylamines with triethylamine as a base and tert-butyl hydroperoxide (TBHP) as oxidant is reported in this paper. The reaction is general, practical, inexpensive, non-toxic, and the method followed is environmentally benign, with moderate to good yields. [Figure not available: see fulltext.]
- Botla, Vinayak,Barreddi, Chiranjeevi,Daggupati, Ramana V,Malapaka, Chandrasekharam
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p. 1469 - 1473
(2016/09/19)
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- Room-temperature copper-catalyzed arylation of dimethylamine and methylamine in neat water
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The first room-temperature copper-catalyzed arylations of dimethylamine and methylamine in neat water have been developed. Using a combination of CuI and 6,7-dihydroquinolin-8(5 H)-one oxime as catalyst, dimethylamine is arylated with various aryl halides to give the corresponding products in good to excellent yields. Further, this catalysis enables the selective arylation of methylamine to afford the high yields of monoarylated methylamines as the sole products.
- Wang, Deping,Kuang, Daizhi,Zhang, Fuxing,Yang, Chunlin,Zhu, Xiaoming
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supporting information
p. 714 - 718
(2015/03/18)
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- Ruthenium-Catalyzed Monoalkenylation of Aromatic Ketones by Cleavage of Carbon-Heteroatom Bonds with Unconventional Chemoselectivity
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Ruthenium-catalyzed selective monoalkenylation of ortho C-O or C-N bonds of aromatic ketones was achieved. The reaction allowed the direct comparison of the relative reactivities of the cleavage of different carbon-heteroatom bonds, thus suggesting an unc
- Kondo, Hikaru,Akiba, Nana,Kochi, Takuya,Kakiuchi, Fumitoshi
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supporting information
p. 9293 - 9297
(2015/08/06)
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- Gold-Catalyzed Reductive Transformation of Nitro Compounds Using Formic Acid: Mild, Efficient, and Versatile
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Developing new efficient catalytic systems to convert abundant and renewable feedstocks into valuable products in a compact, flexible, and target-specific manner is of high importance in modern synthetic chemistry. Here, we describe a versatile set of mild catalytic conditions utilizing a single gold-based solid catalyst that enables the direct and additive-free preparation of four distinct and important amine derivatives (amines, formamides, benzimidazoles, and dimethlyated amines) from readily available formic acid (FA) and nitro starting materials with high level of chemoselectivity. By controlling the stoichiometry of the employed FA, which has attracted considerable interest in the area of sustainable chemistry because of its potential as an entirely renewable hydrogen carrier and as a versatile C1 source, a facile atom- and step-efficient transformation of nitro compounds can be realized in a modular fashion. Renewable formic acid as a flexible feedstock: A versatile heterogeneous gold-based catalytic system has been developed for the controlled, flexible, and target-specific reductive transformation of nitro compounds using stoichiometric equivalents of formic acid as a key starting material under mild and convenient conditions. The overall operational simplicity, high chemoselectivity, functional-group tolerance, and reusability of the catalyst make this approach an attractive and reliable tool for organic and process chemists.
- Yu, Lei,Zhang, Qi,Li, Shu-Shuang,Huang, Jun,Liu, Yong-Mei,He, He-Yong,Cao, Yong
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p. 3029 - 3035
(2015/09/28)
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- Iron(III)-catalyzed C-H functionalization: Ortho-benzoyloxylation of N,N-dialkylanilines and its application to 1,4-benzoxazepines
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A C-O bond-formation reaction that proceeds through C-H functionalization of N,N-dialkylanilines at the ortho-position is presented. The iron-catalyzed selective ortho-benzoyloxylation follows a polar Friedel-Crafts-like mechanism and is sensitive to the nucleophilicity of the anilines. The benzoyl-oxylation of a variety of N,N-disubstituted anilines and Nphenyl heterocycles is carried out under extremely mild conditions. Furthermore, the methodology has been successfully employed for the generation of 1,4-benzoxazepines and oaminophenols.
- Chiranjeevi, Barreddi,Vinayak, Botla,Parsharamulu, Thupakula,PhaniBabu, Vemulapalli S.,Jagadeesh, Bharatam,Sridhar, Balasubramanian,Chandrasekharam, Malapaka
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p. 7839 - 7849
(2015/01/16)
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- Metal-free functionalization of N, N-dialkylanilines via temporary oxidation to N, N-dialkylaniline N-oxides and group transfer
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A simple set of protocols for the controlled elaboration of anilines is reported allowing access to a diverse array of aminophenols, aminoarylsulfonates, alkylated anilines, and aminoanilines in 29-95% yield in a single laboratory operation from easily isolable, bench-stable N,N-dialkylaniline N-oxides. The introduction of new C-O, C-C, and C-N bonds on the aromatic ring is made possible by a temporary increase in oxidation level and excision of a weak N-O bond.
- Lewis, Robert S.,Wisthoff, Michael F.,Grissmerson,Chain, William J.
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supporting information
p. 3832 - 3835
(2014/08/05)
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- Carbon Dioxide Reduction to Methylamines under Metal-Free Conditions
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The first metal-free catalysts are reported for the methylation of amines with carbon dioxide. Proazaphosphatrane superbases prove to be highly active catalysts in the reductive functionalization of CO2, in the presence of hydroboranes. The new methodology enables the methylation of N-H bonds in a wide variety of amines, including secondary amines, with increased chemoselectivity. Organocatalysis: Proazaphosphatrane superbases prove to be highly active catalysts in the reductive functionalization of CO2, in the presence of hydroboranes. The new method makes possible the methylation of N-H bonds in a wide variety of amines, including secondary amines (see picture), with increased chemoselectivity.
- Blondiaux, Enguerrand,Pouessel, Jacky,Cantat, Thibault
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p. 12186 - 12190
(2016/02/23)
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- Catalytic methylation of aromatic amines with formic acid as the unique carbon and hydrogen source
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A novel methodology is presented for the direct methylation of amines, using formic acid as a unique source of carbon and hydrogen. Based on ruthenium(II) catalysts, the formation of the N - CH3group proceeds via an efficient formylation/transfer hydrogenation pathway.
- Savourey, Solne,Lefvre, Guillaume,Berthet, Jean-Claude,Cantat, Thibault
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supporting information
p. 14033 - 14036
(2015/02/19)
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- General catalytic methylation of amines with formic acid under mild reaction conditions
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A general catalytic protocol for the methylation of amines has been developed applying, for the first time, formic acid as the C1 building block and silanes as reducing agents. A broad range of aromatic and aliphatic, both primary and secondary, amines has been converted to the corresponding tertiary amines including [N-13C]-labelled drugs in good to excellent yields under mild conditions. Methylation made easy: A general catalytic protocol for the methylation of amines has been developed applying, for the first time, formic acid as the C1 building block and silanes as reducing agents. A broad range of aromatic and aliphatic, both primary and secondary, amines has been converted to the corresponding tertiary amines, including [N-13C]-labelled drugs, in good to excellent yields at mild conditions (see scheme; dppp=(1,3-bis(diphenylphosphino)propane)).
- Sorribes, Ivan,Junge, Kathrin,Beller, Matthias
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supporting information
p. 7879 - 7883
(2014/07/07)
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- Selective methylation of amines with carbon dioxide and H2
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Put a label on it: Carbon dioxide with H2 is shown to be an efficient and selective methylation reagent for aromatic and aliphatic amines (see scheme; acac=acetylacetonate, triphos = 1,1,1- tris(diphenylphosphanylmethyl)ethane). A variety of functionalized amines including 13C-labelled drugs were obtained with good yields and functional-group tolerance. Copyright
- Li, Yuehui,Sorribes, Ivan,Yan, Tao,Junge, Kathrin,Beller, Matthias
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supporting information
p. 12156 - 12160
(2013/12/04)
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- CO2 as a C1-building block for the catalytic methylation of amines
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A novel catalytic reaction has been designed to utilize, for the first time, CO2 as a C1 feedstock in the synthesis of N-methylamines. Simple zinc catalysts, based on commercially available zinc salts and ligands, prove highly efficient in promoting both a 6 electron reduction of carbon dioxide and the formation of a C-N bond, using hydrosilanes and amines.
- Jacquet, Olivier,Frogneux, Xavier,Das Neves Gomes, Christophe,Cantat, Thibault
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p. 2127 - 2131
(2013/05/21)
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- Substrate-selective dehydrocondensation at the interface of micelles and emulsions of common surfactants
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Scratch the surface: Dehydrocondensations between carboxylates and amines by using an amphiphilic 1,3,5-triazinylammonium-based coupling agent were accelerated by the interfacial effect of micelles and emulsions of common surfactants (see figure). The reaction of carboxylates was promoted by both anionic and nonionic surfactants, and that of amines was promoted by only a nonionic surfactant. High selectivities for more lipophilic substrates were observed in micelles or emulsions. Copyright
- Kunishima, Munetaka,Kikuchi, Kanako,Kawai, Yukio,Hioki, Kazuhito
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supporting information; scheme or table
p. 2080 - 2083
(2012/05/20)
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- Insertion of arynes into the carbon-oxygen double bond of amides and its application into the sequential reactions
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The reaction of arynes, generated from ortho-(trimethylsilyl)aryl triflates, with the CO bond of formamides gave salicylaldehyde derivatives via the formation of formal [2+2] adducts. The sequential transformation of arynes into ortho-disubstituted arenes, o-aminoalkylphenols or o-hydroxyalkylphenols, was achieved by one-pot procedure using dialkylzincs.
- Yoshioka, Eito,Miyabe, Hideto
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experimental part
p. 179 - 189
(2012/02/15)
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- N -heterocyclic carbene-palladium(II)-1-methylimidazole complex catalyzed amination between aryl chlorides and amides
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We report herein that amides are excellent N-sources in the NHC-Pd(II)-Im complex 1 catalyzed amination of aryl chlorides. In the presence of KO tBu, various aryl chlorides and amides can react smoothly to give the corresponding aminated products in moderate to almost quantitative yields at room temperature within 6 h.
- Chen, Wen-Xin,Shao, Li-Xiong
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p. 9236 - 9239,4
(2012/12/12)
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- N -heterocyclic carbene-palladium(II)-1-methylimidazole complex catalyzed amination between aryl chlorides and amides
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We report herein that amides are excellent N-sources in the NHC-Pd(II)-Im complex 1 catalyzed amination of aryl chlorides. In the presence of KO tBu, various aryl chlorides and amides can react smoothly to give the corresponding aminated products in moderate to almost quantitative yields at room temperature within 6 h.
- Chen, Wen-Xin,Shao, Li-Xiong
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p. 9236 - 9239
(2013/01/15)
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- New deoxygenation method for amine n-oxides using dimethylthiocarbamoyl chloride
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A facile and efficient deoxygenation method for various amine N-oxides to their corresponding amines is described. The experimental procedure is quite simple and the products are obtained in excellent yields. Copyright Taylor & Francis Group, LLC.
- Caliskan, Hafize,Zaim, Oemer
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experimental part
p. 3078 - 3083
(2010/11/04)
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- Selective monomethylation of anilines by Cu(OAc)2-promoted cross-coupling with MeB(OH)2
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N-Methylanilines are readily synthesized in high yields through the copper(ll)-promoted coupling of anilines and methylboronic acid. This method represents a new approach for the selective monomethylation of anilines, and it is the first reported example
- Gonzalez, Israel,Mosquera, Jesus,Guerrero, Cesar,Rodriguez, Ramon,Cruces, Jacobo
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supporting information; experimental part
p. 1677 - 1680
(2009/09/06)
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- On the mechanism of the N,N-dimethyl amination of Grignard reagents: A kinetic study
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A direct kinetic study is reported for the electrophilic amination of substituted phenylmagnesium bromides with N,N-dimethyl O-(mesitylenesulfonyl) hydroxylamine in THF. Rate data, Hammett relationship, and activation entropy are consistent with a SN2 displacement involving the attack of carbanions to sp3N in the amination reagent (AR). Copyright
- Erdik, Ender,Uelhue, Selma Ates
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p. 671 - 676
(2008/03/12)
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- PROCESS FOR THE SYNTHESIS OF ARYLAMINES FROM THE REACTION OF AN AROMATIC COMPOUND WITH AMMONIA OR A METAL AMIDE
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A catalytic process for the synthesis of aromatic primary amines, reagent compositions for effecting the process, and transition metal complexes useful in the process, are provided.
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Page/Page column 60-61
(2008/06/13)
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- Synthesis of N,N-dimethylamines via Barbier-Grignard-type electrophilic amination
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Aryl Grignard reagents react with N,N-dimethyl O-(mesitylenesulfonyl)- hydroxylamine in THF under Barbier conditions at room temperature and give N,Ndimethylanilines with high yields in a 2-h reaction. The amination yield of in situ Grignard reagents were not lower than those of preformed aryl Grignard reagents. In situ cycloalkyl-, allyl-, and benzylmagnesium bromides did not react with N,Ndimethyl O-(mesitylenesulfonyl)hydroxylamine, except that amination of in situ n-hexylmagnesium bromide resulted in a medium yield. Grignard-Barbier-type amination of aryl bromides with N,N-dimethyl O-(mesitylenesulfonyl)hydroxylamine provides a new alternative route for the synthesis of N,N-dimethylanilines. Copyright Taylor & Francis Group, LLC.
- Erdik, Ender,Ates, Selma
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p. 2813 - 2818
(2007/10/03)
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- Influence of intramolecular hydrogen bonding on the conformational equilibrium of cis-3-N,N-dimethylaminocyclohexanol compared with trans-3-N,N-dimethylaminocyclohexanol and cis- and trans-3-N,N-dimethylamino-1- methoxycyclohexane
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1H NMR data show that concentration increase shifts the conformational equilibrium of cis-3-N,N-dimethylaminocyclohexanol (1) (cis-3-DACH) from the 1aa conformer, stabilized by an intramolecular hydrogen bond (IAHB), to the lee conformer [43% (
- De Oliveira,Ribeiro,Rittner
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p. 513 - 521
(2007/10/03)
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- Oxyaniliniums as acetylcholinesterase inhibitors for the reversal of neuromuscular block
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A series of oxyanilinium-based AChE inhibitors have been synthesised and tested for the reversal of vecuronium-induced neuromuscular block. Several compounds, for example 2-hydroxy- and 2-methoxy-N,N-dimethyl-N-allylanilinium bromide (3 and 6) showed comparable reversal potencies to edrophonium and clean in vivo cardiovascular profiles.
- Grove, Simon J.A.,Kaur, Jasmit,Muir, Alan W.,Pow, Eleanor,Tarver, Gary J.,Zhang, Ming-Qiang
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p. 193 - 196
(2007/10/03)
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- Preparation of arylamines
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A method of preparing an arylamine compound includes reacting a metal amide comprising a metal selected from the group consisting of tin, boron, zinc, magnesium, indium and silicon, with an aromatic compound comprising an activated substituent in the pres
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