22014-90-0Relevant articles and documents
Cp*Ir complex bearing a flexible bridging and functional 2,2′-methylenebibenzimidazole ligand as an auto-tandem catalyst for the synthesis of N-methyl tertiary amines from imines via transfer hydrogenation/N-methylation with methanol
Ai, Yao,Chen, Xiaozhong,Li, Feng,Liu, Peng,Yang, Chenchen,Yang, Jiazhi
, p. 325 - 334 (2021/10/07)
A Cp*Ir complex bearing a flexible bridging and functional 2,2′-methylenebibenzimidazole ligand was designed, synthesized, and found to be a general and efficient auto-tandem catalyst for the synthesis of N-methyl tertiary amines from imines via transfer hydrogenation/N-methylation with methanol as both hydrogen source and methylating reagent. In the presence of [Cp*Ir(2,2′-CH2BiBzImH2)Cl][Cl], a range of desirable products were obtained in high yields with nearly complete selectivities. The reaction is highly attractive due to the highly atom economy, and minimal consumption of chemicals and energy. Notably, this research exhibits new potential of metal–ligand bifunctional catalysts for the activation of methanol as C1 source for organic synthesis.
Synthesis of Lactams by Reductive Amination of Carbonyl Derivatives with ω-Amino Fatty Acids under Hydrosilylation Conditions
Tongdee, Satawat,Wei, Duo,Wu, Jiajun,Netkaew, Chakkrit,Darcel, Christophe
, p. 5536 - 5539 (2021/08/07)
An efficient method for the preparation of lactams from ω-amino fatty acids under hydrosilylation is described. A variety of lactams such as pyrrolidinones, piperidinones and 2-azepanones were selectively synthesised in moderate to excellent yields (29 examples, up to 95 % isolated yields) with a good functional group tolerance. Notably, no metallic based catalyst was required to perform this transformation.
An Efficient Palladium-Catalysed Aminocarbonylation of Benzyl Chlorides
Oram, Niall,Richardson, Jeffery,Rilvin-Derrick, Eloise
, p. 369 - 372 (2020/02/27)
An improved procedure for the aminocarbonylation of benzyl chloride derivatives using carbon monoxide and either primary or secondary amines has been developed. Studying the competing background alkylation reaction allowed the solvent and base to be selected for a simple catalyst screen, which, in turn, enabled the discovery of a method for the preparation of 2-arylacetamides under mild conditions, with minimal side-products using an inexpensive phosphine ligand. This non-traditional optimisation strategy allowed us to overcome the background alkylation, which has been cited as justification for the development of more complex and less atom-economical approaches.
REACTIONS OF STANNYL CATIONS
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Page/Page column 22, (2018/01/17)
The present invention relates to a method of reducing, cleaving and/or coupling at least one C=O, C-O, C=C or C=N bond of a compound, using a reagent comprising a stannyl cation.
Ruthenium-catalyzed deaminative redistribution of primary and secondary amines
Kostera,Wyrzykiewicz,Pawlu?,Marciniec
, p. 11552 - 11555 (2017/09/18)
A ruthenium-hydride complex, [Ru(H)(Cl)(CO)(PCy3)2], was found to be active in the highly selective redistribution of primary and secondary amines bearing an α-hydrogen atom. This new deaminative coupling of amines enables the highly selective synthesis of secondary amines from primary amines and of tertiary amines from secondary amines with the evolution of ammonia. A preliminary mechanistic view of this novel reaction based on catalytic experiments using NMR methods confirms the synthetic observations.
Colloid and nanosized catalysts in organic synthesis: XIV. Reductive amination and amidation of carbonitriles catalyzed by nickel nanoparticles
Popov, Yu. V.,Mokhov,Shcherbakova
, p. 798 - 805 (2016/06/13)
Hydrogenation of carbonitriles catalyzed by nickel nanoparticles in the presence of primary amines led to the predominant formation of unsymmetrical secondary amines. In the presence of secondary amines hydrogenation of nitrites provided enamines as main products. Hydrogenation of nitriles in the presence of formamide or acetamide afforded formyl or acetyl derivatives of primary amines.
A process for preparing amine compound using carbon-supported cobalt-rhodium nanoparticel catalyzed hydrogen-free recuctive amination
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Paragraph 0066; 0069; 0073, (2017/04/25)
The present invention relates to hydrogen-free reductive amination of an aldehyde and/or ketone and an amine and/or nitroarene using cobalt-rhodium heterometal nanoparticles supported on carbon as a non-homogeneous catalyst. According to the present invention, it is possible to carry out amination under significantly lower pressure as compared to the reductive amination carried out in the presence of a conventional rhodium or ruthenium catalyst. In addition, there is no need for using an additional ligand, acid or base. Further, it is possible to use water generated in a reaction system by a water-gas shift reaction as a hydrogen source with no use of an external hydrogen source, and thus to use a solvent without purification. Thus, it is possible to simplify the reaction procedure. The catalyst system according to the present invention provides a simple method for preparing secondary and tertiary amines from various aldehydes and amines.
Hydrogen-Free Cobalt-Rhodium Heterobimetallic Nanoparticle-Catalyzed Reductive Amination of Aldehydes and Ketones with Amines and Nitroarenes in the Presence of Carbon Monoxide and Water
Park, Jang Won,Chung, Young Keun
, p. 4846 - 4850 (2015/08/18)
Cobalt-rhodium heterobimetallic nanoparticle-catalyzed reductive amination of aldehydes and ketones with amines in the presence of 5 atm carbon monoxide without an external hydrogen source has been developed. Water added and generated in situ produces hydrogen via a water-gas-shift reaction. The reaction can be extended to the tandem reduction of aldehydes and ketones with nitroarenes. The catalytic system is stable under the reaction conditions and could be reused eight times without losing any catalytic activity. (Chemical Equation Presented).
N-alkylation of amines by homogeneous ruthenium complexes in the presence of free diphosphines
Tamaddoni Jahromi, Bahareh,Kharat, Ali Nemati
, p. 3498 - 3508 (2014/01/06)
Chemoselective N-alkylation of amines by ruthenium complexes in the presence of free diphosphine ligands under mild conditions is described. Octyl amine and aniline were chosen as aliphatic and aromatic amines to investigate the effect of different phosphines, reaction times, and temperature on conversion, as well as selectivity towards related secondary and tertiary amines. After optimization of the reaction conditions, this catalytic system was used for N-alkylation of other amines and has shown moderate to very good yields. The reaction products were monitored by GC-MS. The crystal structure of [Ru(NO3)2CO(PPh3)2] with a monodentate and a bidentate nitrate was determined by X-ray crystallographic analysis.
Nonlinear taft polar free energy relationship: Reactions of N-substituted benzyl amines with benzyl bromide in methanol
Ravi,Sanjeev,Jagannadham
, p. 803 - 810 (2013/11/19)
The rates of reactions of N-substituted benzyl amines with benzyl bromide were measured using a conductivity technique in methanol medium. The reaction followed a total second-order path. The end product of the reaction is identified as dibenzyl alkyl amine (C6H5CH 2N(R)CH2C6H5). The rates increased with a decrease in the electron-donating capacity or with an increase in the Taft σ* value of electron-donating alkyl substituents (R) such as t-butyl (σ* = -0.3), i-propyl (σ* = -0.19), n-butyl (σ* = -0.13), and ethyl (σ* = -0.1) on nitrogen of the amine until the Taft σ* value becomes zero for the methyl group (σ CH 3* = 0.00), and then the rates decreased with an increase in the electron-withdrawing capacity or with an increase in the Taft σ* value of electron-withdrawing substituents (R) such H and C6H 5 (σH* = 0.49 and σC6H5= 0.6). The locus of the Taft polar free energy relationship has a maximum near the point for N-methyl benzyl amine, showing that there is a sharp change in the rate-determining step. A mechanism involving formation of an SN2-type transition state between the amine nucleophiles and the benzyl bromide and its subsequent decomposition is proposed. Activation parameters were calculated and are discussed.
