Highly Efficient <i>N</i>‐Monomethylation of Primary Aryl Amines

Peng, Yiyuan; Liu, Hanliang; Tang, Min; Cai, Lisheng; Pike, Victor W.

doi:10.1002/cjoc.200990224

Cited by 18 publications

(14 citation statements)

References 35 publications

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“…The X-ray study of G 1 -COOCH 3 shows that the three dendrons have large but proper volumes as the fine ligands of Brookhart's catalyst. The amides prepared by ammonolysis of G 1 -COOCH 3 in high yields have been readily converted to the corresponding amines using sodium hypochlorite as the oxidant.…”

Section: Resultsmentioning

confidence: 99%

“…7 mL of 9% NaOCl (Chlorox) plus carboxamide 3,4,5-G 1 -CONH 2 (2.0 mmol) was added into this magnetically stirred mixture, with the former being added drop-wise. The mixture was allowed to be warmed to room temperature and then stirred intensively for 30 min to produce the intermediate carbamate 3,4,5-G 1 -NHCO 2 CH 3 . A solution of NaOH (40 mmol) in MeOH (10 mL) and water (2 mL) was added, and the whole mixture was heated under reflux for 4 d. The obtained solution was cooled to room temperature and then the solvent was evaporated in vacuum to separate out the precipitate.…”

Section: General Procedures For the Synthesis And Purification Of G 1 mentioning

confidence: 99%

“…Aromatic amines are important synthetic intermediates that play a central role in many areas such as polymer and medicine, [1][2][3][4] which can be produced by the reduction of the corresponding nitro aromatic with a metallo hydride reagent or by catalytic hydrogenation. 5 The selective reduction of aromatic nitro groups in the presence of sensitive functional groups, e.g.…”

Section: Introductionmentioning

confidence: 99%

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Design and Synthesis of Two Aromatic Amines with Dendritic Structure

Luo

Chen

2010

Chin. J. Chem.

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The design and synthesis of two aromatic amines with dendritic structures, i.e. 3,4,5-tribenzyloxyaniline (3,4,5-G(1)-NH2) and 2,5-dibenzyloxyaniline (2,5-G(1)-NH2), were conducted. A coupling reaction of three or two equivalents of benzyl bromide to one equivalent of methyl hydroxybenzoate generated methyl 3,4,5-tribenzyloxybenzoate (3,4,5-G(1)-COOCH3), methyl 2,5-dibenzyloxybenzoate (2,5-G(1)-COOCH3) and 2,6-dibenzyloxybenzoate (2,6-G(1)-COOCH3) in high yields. All G(1)-COOCH3 derivatives were studied by X-ray analysis. The results show that these dendrons have sufficient volume to be used as the fine ligands for certain catalysts. The amide intermediates (benzamide, G(1)-CONH2) were obtained by reaction between ammonia and G(1)-COOCH3. Interestingly, 2,6-dibenzyloxybenzamide (2,6-G(1)-CONH2) can not be prepared in the same condition, which may be due to the overlarge steric block. Sodium hypochlorite was an effective oxidant to generate methyl carbamates G(1)-NHCO2CH3.National Natural Science Foundation of China [20406016]; State Key Laboratory of Physical Chemistry of Solid Surface (Xiamen University

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Section: Resultsmentioning

confidence: 99%

Section: General Procedures For the Synthesis And Purification Of G 1 mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Design and Synthesis of Two Aromatic Amines with Dendritic Structure

Luo

Chen

2010

Chin. J. Chem.

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“…The mixture was concentrated to dryness, anhydrous pentane (100 mL) was added and the resulting colorless solid was filtered, washed with anhydrous pentane (2 50 mL) and dried in vacuo to yield 3 c as a colorless solid (10.5 N-Methyl-4-iodoacetanilide (4 v): A modified literature procedure was followed. [30] A 100 mL round-bottomed Schlenk flask with a rubber septum was charged with sodium hydride suspension in mineral oil (60 %, 480 mg, 12 mmol), which was washed with anhydrous pentane (20 mL), and evacuated and refilled with nitrogen three times. A solution of 4-iodoacetanilide (2.61 g, 10.0 mmol) in anhydrous THF (50 mL) was added and the mixture was stirred for 15 min.…”

Section: Methodsmentioning

confidence: 99%

Copper‐Catalyzed Trifluoromethylation of Aryl Iodides with Potassium (Trifluoromethyl)trimethoxyborate

Knauber

Arikan

Röschenthaler

et al. 2011

Chemistry A European J

266

107

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Potassium (trifluoromethyl)trimethoxyborate is introduced as a new source of CF(3) nucleophiles in copper-catalyzed trifluoromethylation reactions. The crystalline salt is stable on storage, easy to handle, and can be obtained in near-quantitative yields simply by mixing B(OMe)(3), CF(3)SiMe(3), and KF. The trifluoromethylation reagent allows the conversion of various aryl iodides into the corresponding benzotrifluorides in high yields under mild, base-free conditions in the presence of catalytic quantities of a Cu(I)/1,10-phenanthroline complex.

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“…To achieve the N‐monomethylated product, Krein and Lowary reported an efficient route for the preparation of 2‐(methylamino)pyridine 161 from the readily accessible intermediate 159 . Similarly, Peng and co‐workers described a convenient protocol to access the N‐monomethylated aniline 164 from the acetamide intermediate 162 (Scheme ) …”

Section: N‐methylationmentioning

confidence: 99%

Advances in the Synthesis of Methylated Products through Indirect Approaches

Chen

2019

Adv Synth Catal

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Methylation is a well‐known structural modification in organic and medicinal chemistry. In addition to using conventional methylation reagents for direct methylation, indirect methylation approaches have been also successfully applied, particularly to tackle the isolation difficulty among the methylated product, the unreacted starting material, and the dimethylated by‐product due to the structural similarities between them. This review summarizes recent advances in the synthesis of methylated products through indirect approaches – transforming functionalized intermediates into the methylated products. The indirect methodologies surveyed in this review are useful for chemists to select appropriate methylation strategies, particularly for the challenging synthesis of methylated products at a large scale in drug discovery. Abbreviations: AIBN: azobisisobutyronitrile; Cbz: carbobenzyloxy; DBU: 1,8‐diazabicyclo[5.4.0]undec‐7‐ene; DIBAL: diisobutylaluminium hydride; FA: formic acid; Fmoc: fluorenylmethyloxycarbonyl; KOTMS: potassium trimethylsilanolate; LAH: lithium aluminium hydride; LiHBEt3: lithium triethylborohydride; PC: photocatalyst; PMHS: polymethylhydrosiloxane; PSMS: zinc bis(phenylsulfonylmethanesulfinate); SAM: S‐adenosylmethionine; SET: single electron transfer; TBAF: tetra‐n‐butylammonium fluoride; TBS: tert‐butyldimethylsilyl; TEA: trimethylamine; TFA: trifluoroacetic acid; TMS: trimethylsilyl; Ts: 4‐toluenesulfonyl.

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Highly Efficient N‐Monomethylation of Primary Aryl Amines

Cited by 18 publications

References 35 publications

Design and Synthesis of Two Aromatic Amines with Dendritic Structure

Design and Synthesis of Two Aromatic Amines with Dendritic Structure

Copper‐Catalyzed Trifluoromethylation of Aryl Iodides with Potassium (Trifluoromethyl)trimethoxyborate

Advances in the Synthesis of Methylated Products through Indirect Approaches

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