N-methylation versus oxidative addition using MeI in the reaction of organoplatinum(II) complexes containing pyrazine ligand

Fatemeh, Niroomand Hosseini; Farasat, Zahra; Nabavizadeh, S. Masoud; Abu‐Omar, Mahdi M.

doi:10.1016/j.jorganchem.2018.11.002

Cited by 12 publications

(8 citation statements)

References 27 publications

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“…When the substituent group on the para position changed from H to Methyl, Ethyl, t Butyl, excellent selectivity was obtained for all the phenylmethanamine substrates (1-4). The important building blocks halo-substituted aromatic amines, no matter where the halogen is located, were successfully transformed to the corresponding tertiary amines in excellent selectivity (5)(6)(7)(8). The biomass platform derivatives amines compounds (9-13) were well tolerated under modi ed reaction conditions to give the N, N-di-methylamines products in good to excellent yield.…”

Section: Resultsmentioning

confidence: 99%

“…Speci cally, according to the reported top 200 pharmaceuticals by Retail Sales in 2020, among the showing chemical structure 120 pharmaceuticals, there are 110 drugs containing nitrogen and/or amino groups which are amine derivatives 6 . So far, a lot of researchers have developed many advanced methodologies for the synthesis of amines using alkyl halides benzenes 7 , formaldehyde 8 , paraformaldehyde 9 , methanol 10 , dimethyl sulfoxide 11 , dimethyl carbonate 12 , and CO 2 2,13 as methylation agents. However, most of the traditional N-methylation synthesis methods of amines suffer from operationally problematic, narrow amines substrates scopes, toxic methylation reagents, and production of a large amount of waste, which is against the economic, atomic, and sustainable chemistry process requirements.…”

Section: Introductionmentioning

confidence: 99%

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Facile synthesis of N-doped graphene encapsulated Pd@N/C catalyst and its efficient application in cascade flow synthesis of amines

Liu¹,

Sun²,

Song³

et al. 2021

Preprint

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N-methylamines, as an important class of chemicals, crucial building blocks, have been widely used in pharmaceutical companies and materials synthesis. Transition metal-catalyzed synthesis of N-methylamines, especially the heterogeneous catalyzed N-methylation of amines via different C1 sources has become the most promising methodology, due to the environmentally friendlier process and the recyclable and easily accessible catalysts. However, these reactions generally require activated toxic methyl iodide or dimethyl sulfoxide, and homogeneous catalysts or Raney nickel catalyst. The synthesis of amines still suffering from narrow scopes of amines, harsh reaction conditions, low selectivity of the desired products, and against the requirements of atomic economy and sustainable green environment. Herein, we developed a novel facile synthesis of nitrogen-doped graphene encapsulated Pd@NC nanocatalysts. The resulting heterogeneous catalyst was active for the synthesis of amines (more than 83 examples, yield up to 99%). The nitrogen-doped effect was unlike the previous report that poisoned the metal, it could increase the interaction with the active metal resulting in excellent stability. As far as we know, for the first time, the developed N-doped graphene encapsulated Pd@NC nanocatalyst showed excellent stability and activity of amines synthesis in the 20 times’ recycling test, industrially applicable flow reactor 2880 minutes’ test, and 99% purity of primary amine and tertiary amines product preparation test. Moreover, we have also shown the high atomic economy and environmentally friendlier tandem flow synthesis of N, N-dimethylamine products via the combination of reduction of nitrobenzene and N-methylation of amines, using the single one Pd@NC nanocatalyst with H2O as the only by-product. Upon our knowledge, this is a novel example of primary amine and tertiary amine synthesis methodology with the combined cascade reaction and flow process of nitrobenzene reduction and primary amines N-methylation with a single heterogeneous catalyst.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Facile synthesis of N-doped graphene encapsulated Pd@N/C catalyst and its efficient application in cascade flow synthesis of amines

Liu¹,

Sun²,

Song³

et al. 2021

Preprint

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“…Similarly, encouraged by the successful synthesis of tertiary amine by the N-methylation of primary or secondary amines with formaldehyde catalyzed with catalyst H, we kept on exploring the synthesis of tertiary amine starting from primary, secondary amines or dimethylamine and diethylamine with different functional substituted aldehydes, which were seldom reported previously. To our delight, most of the aromatic primary and secondary amines were converted to the corresponding tertiary amines in moderate to excellent yields using different functional aromatic, aliphatic, cyclic, heterocyclic aldehydes (38)(39)(40)(41)(42)(43)(44)(45)(46)(47)(48)(49). To the best of our knowledge, few works reported the synthesis of tertiary amines using secondary amines and functional aldehydes via transition metal catalyzed N-methylation method.…”

Section: Resultsmentioning

confidence: 99%

“…Since N-methylated amines exist widely as bioactive compounds, pharmaceutical drugs, and so on, the development of more efficient, environmentally friendly, economical, and sustainable N-methylation processes attracted chemists' attention continuously over the last decades 3,4,6,8,[15][16][17][18][19][20][21][22][23][24][25][26] . Until then, many methodologies for the synthesis of N-methylamines have been developed and widely used in academics and industry, applying formaldehyde 27 , CO2 4,6,26,28,29 , alcohols (mostly methanol) [30][31][32] , paraformaldehyde 33,34 , dimethyl sulfoxide (DMSO) 35,36 , dimethyl carbonate 37,38 , alkyl halides or halogenated benzenes 39,40 as methylation agents. Traditional N-methylation reactions generally encounter drawbacks including narrow scopes of amines, operationally problematic, and generation of by-products; this process may also cause a large amount of waste since the utilization of some of the activated methyl compounds, such as toxic methyl iodide, dimethyl sulfoxide, or dimethyl carbonate, is not recommendable.…”

Section: Introductionmentioning

confidence: 99%

Efficient, Green, and Renewable N-Di-Methylation Synthesis of Amines by a Novel Nano-Catalyst of NiNiO@C

Liu

Song²,

Zhuang³

et al. 2021

Preprint

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<a></a><a>The development of Earth-abundant reusable and no-toxic heterogeneous catalyst applied in the pharmaceutically, bio-active relevant compounds synthesis as well as other organic syntheses still remains as the most important goal of the general chemical research. N-methylated compounds, as one of the most essential bioactive compounds,</a> have been widely used in the fine and bulk industries for the production of high-value chemicals including pharmaceuticals, agrochemicals, and dyes. As their reports, activated toxic methyl iodide and dimethyl sulfoxide were usually employed in the traditional N-methylation, which easily suffer from narrow scopes of amines, generation of by-products, and a large amount of waste. <a>Very recently, </a>transition metal-catalyzed methylation of amines has become an efficient, practical, and cost-effective method for the one-pot selective synthesis of N-methylamines with C1 sources. Herein, we first developed a simple and <a>environmentally friendly</a> method for the preparation of efficient, reusable, and low-cost graphene spheres encapsulated Ni/NiO nanoalloy catalysts (Ni/NiO@C) for highly selective synthesis of the N-methylated compounds by using various functional amines and aldehydes under easily handle-able and industrially <a></a><a>applicable </a>conditions. A large number of primary, secondary amines (more than 70 examples) could be converted smoothly to the corresponding N, N-dimethylamines with the participation of different functional aldehydes. The gram-scale synthesis was also demonstrated in an excellent yield; not only that, the catalyst was further proved that it could be easily recycled by its intrinsic magnetism and reused up to ten times without losing activity and selectivity. Both of them are the great advantages in contrast to other catalysts reported previously. And also, for the first time, we have developed the highly efficient, cost-effective tandem synthesis of N, N-dimethylamines products in a one-pot process by means of aldehydes and NH3. As far as we know, this is the first example of the synthesis of tertiary amines with the combined reaction process of reductive amination of aldehydes and N-methylation of primary amines only with the single one earth-abundant metal catalyst. Overall, the advantages of this newly developed method including operational simplicity, high stability, easily recyclable, cost-effective of the catalyst, and good functional group compatibility for the synthesis of N-methylation products, as well as the highly efficient and industrial applicable tandem synthesis process.

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“…N-methylamine is a high-value chemical product, which is widely used in the fields of drugs, bioactive products, dyes, preservatives, and agrochemicals [1][2][3][4][5][6][7][8]. Traditional synthesis methods require toxic and dangerous stoichiometric reagents, such as halogenated methane [9], dimethyl sulfate [10], or diazomethane [11]. Reactions using these reagents produce a large amount of waste and exhibit low selectivity due to excessive alkylation to N, N-dimethylamine.…”

Section: Introductionmentioning

confidence: 99%

Facile synthesis of novel heterogenous Rh/COF catalyst and its application in tandem selective transfer hydrogenation and mono-methylation of Nitro compounds with Methanol

Liu¹,

Zhang

Wang

et al. 2021

Preprint

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The development of transition metal heterogeneous catalysts for economical and effective synthesis of N-methylamine, especially for the mono-methylation of amines is still challenging. Herein, two unprecedented Rh-supported COFs heterogeneous catalysts Rh/MelCOF was facile synthesized by Schiff base reaction using melamine as a precursor, and for the first time, it was successfully applied to the effective and high selective tandem reaction of transfer hydrogenation and mono-methylation of nitroaromatic hydrocarbons with methanol as C1 and hydrogenation source, with water as the only by-product. A series of nitroaromatic hydrocarbons, including heterocyclic or sterically hindered derivatives, can be well tolerated and the catalyst could also be reused 4 times without losing significant reactivity. At the same time, the study of the Rh/MelCOF mechanism supports the hydrogen borrowing mechanism and puts forward the reaction pathway of azobenzene as an intermediate, which is better than the hydrogen transfer pathway from N-phenylhydroxylamine to aniline directly. This work not only expands the COF family but also provides an effective way to obtain mono N-methylated amines from nitroaromatic hydrocarbons, as well as the detailed mechanism of Rh/COF catalyzed tandem transfer hydrogenation and mono-methylation of amines.

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N-methylation versus oxidative addition using MeI in the reaction of organoplatinum(II) complexes containing pyrazine ligand

Cited by 12 publications

References 27 publications

Facile synthesis of N-doped graphene encapsulated Pd@N/C catalyst and its efficient application in cascade flow synthesis of amines

Facile synthesis of N-doped graphene encapsulated Pd@N/C catalyst and its efficient application in cascade flow synthesis of amines

Efficient, Green, and Renewable N-Di-Methylation Synthesis of Amines by a Novel Nano-Catalyst of NiNiO@C

Facile synthesis of novel heterogenous Rh/COF catalyst and its application in tandem selective transfer hydrogenation and mono-methylation of Nitro compounds with Methanol

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