- 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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- 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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- 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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- METHOD FOR THE METHYLATION OF NITROGEN-CONTAINING ORGANIC COMPOUNDS
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A method for the methylation of amines, amides and imines comprises the step of reacting these compounds with CO2 and H2 in the presence of a Ruthenium-phosphine complex.
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Page/Page column 8-9
(2015/01/16)
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- Method for the methylation of nitrogen-containing Organic Compounds
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A method for the methylation of amines, amides and imines comprises the step of reacting these compounds with CO2 and H2 in the presence of a Ruthenium-phosphine complex.
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Paragraph 0039; 0041
(2015/01/18)
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- FLUORINATION OF ORGANIC COMPOUNDS
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Methods for fluorinating organic compounds utilizing a novel organic reagent are described herein. The invention further discloses the utility of this reagent for incorporation of the 18 F isotope into hydroxyl group -containing organic molecules for PET imaging studies. Preparation of the reagents is described along with isolable intermediate structures from reaction of the reagent with a hydroxyl group-containing organic molecule.
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Paragraph 00207
(2015/05/05)
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- Pd-catalyzed nucleophilic fluorination of aryl bromides
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On the basis of mechanism-driven reaction design, a Pd-catalyzed nucleophilic fluorination of aryl bromides and iodides has been developed. The method exhibits a broad substrate scope, especially with respect to nitrogen-containing heteroaryl bromides, and proceeds with minimal formation of the corresponding reduction products. A facilitated ligand modification process was shown to be critical to the success of the reaction.
- Lee, Hong Geun,Milner, Phillip J.,Buchwald, Stephen L.
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supporting information
p. 3792 - 3795
(2014/04/03)
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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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- Studying regioisomer formation in the pd-catalyzed fluorination of aryl triflates by deuterium labeling
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Isotopic labeling has been used to determine that a portion of the desired product in the Pd-catalyzed fluorination of electron-rich, non-ortho-substituted aryl triflates results from direct C-F cross-coupling. In some cases, formation of a Pd-aryne intermediate is responsible for producing undesired regioisomers. The generation of the Pd-aryne intermediate occurs primarily via ortho-deprotonation of a L·Pd(Ar)OTf (L = biaryl monophosphine) species by CsF and thus competes directly with the transmetalation step of the catalytic cycle. Deuterium labeling studies were conducted with a variety of aryl triflates.
- Milner, Phillip J.,Kinzel, Tom,Zhang, Yong,Buchwald, Stephen L.
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supporting information
p. 15757 - 15766
(2015/02/02)
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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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- Ruthenium-catalyzed direct methylation of primary and secondary aromatic amines using carbon dioxide and molecular hydrogen
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The effective catalytic N-methylation of anilines using CO2 as C1 source and molecular hydrogen as reducing agent was demonstrated using the well-defined [Ru(triphos)(tmm)] catalyst. Secondary and primary (shown) aromatic amines were mono- or dialkylated, respectively, in high yields. N-methylation of amides coupled with the amide hydrogenation offers an efficient approach to unsymmetrical tertiary methyl/alkyl/aromatic amines. Copyright
- Beydoun, Kassem,Vom Stein, Thorsten,Klankermayer, Juergen,Leitner, Walter
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supporting information
p. 9554 - 9557
(2013/09/23)
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- FLUORINATION OF ORGANIC COMPOUNDS
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Methods for fluorinating organic compounds are described herein.
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Page/Page column 24
(2012/11/06)
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- Deoxyfluorination of phenols
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An operationally simple ipso fluorination of phenols with a new deoxyfluorination reagent is presented.
- Tang, Pingping,Wang, Weike,Ritter, Tobias
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supporting information; experimental part
p. 11482 - 11484
(2011/10/02)
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- Formation of arf from lpdar(f): catalytic conversion of aryl triflates to aryl fluorides
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Despite increasing pharmaceutical importance, fluorinated aromatic organic molecules remain difficult to synthesize. Present methods require either harsh reaction conditions or highly specialized reagents, making the preparation of complex fluoroarenes ch
- Watson, Donald A.,Su, Mingjuan,Teverovskiy, Georgiy,Zhang, Yong,Garcia-Fortanet, Jorge,Kinzel, Tom,Buchwaldf, Stephen L.
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scheme or table
p. 1661 - 1664
(2010/06/16)
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- PHENOTHIAZIN DERIVATIVES FOR ANTIVIRAL TREATMENTS
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Compounds and methods for preventing and treating viral infections are provided. In some embodiments, novel compounds broad-spectrum antiviral activity are provided. In more specific embodiments, the compounds and methods are effective against viruses such as Venezuelan Equine Encephalitis, West Nile Virus, and Hepatitis C.
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Page/Page column 18
(2008/12/04)
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