Magnesium‐Catalyzed Proficient Reduction of Oximes to Amines Using Ammonium Formate

Abiraj, K.; Gowda, D. Channe

doi:10.1081/scc-120027707

Cited by 24 publications

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“…Oxime ethers, nitriles, and azines were also reduced in the presence of Pd/C [19,22,23]. However, despite diversity of methods for the preparation of benzylamines, there are very limited published data on the synthesis of benzylamines with hydroxy and alkoxy groups in the aromatic ring [11,13,[16][17][18]21].In the present work we examined different synthetic approaches to functionally substituted benzylamines, primarily to those containing hydroxy and alkoxy substituents. In particular, such standard procedures as hydride reduction of aldehyde and ketone oximes with LiAlH 4 , reduction of ketone oximes with sodium in liquid ammonia, and reductive amination of ketones according to Leuckart-Wallach were studied.…”

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“…Benzylamines are usually prepared by reductive amination of carbonyl compounds [8][9][10][11][12] and reduction of the corresponding oximes, nitriles, or azines. Oximes can be reduced with sodium amalgam [13], metallic sodium in liquid ammonia [14,15], Mg-HCOONH 4 -MeOH [16], Raney nickel-EtOH-base [17][18][19], LiAlH 4 [10], NaBH 4 -TiCl 4 [20], and NaBH 4 -LiCl-Amberlyst [21]. Oxime ethers, nitriles, and azines were also reduced in the presence of Pd/C [19,22,23].…”

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Comparison of different reducing systems in the synthesis of functionally substituted benzylamines from alkyl aryl ketones and aromatic aldehydes

et al. 2010

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Different synthetic approaches to functionally substituted benzylamines were examined: reductive amination of alkyl aryl ketones and reduction of aromatic aldehyde oximes. The most efficient procedures were used to prepare a series of previously unknown hydroxy-, alkoxy-, and halogen-substituted benzylamines.Benzylamines are widely used in the synthesis of enzyme inhibitors [1][2][3][4][5] and compounds exhibiting analgesic [3], antithrombotic [2], antibacterial [6], fungicidal [7], and other kinds of biological activity. Benzylamines are usually prepared by reductive amination of carbonyl compounds [8-12] and reduction of the corresponding oximes, nitriles, or azines. Oximes can be reduced with sodium amalgam [13], metallic sodium in liquid ammonia [14, 15], Mg-HCOONH 4 -MeOH [16], Raney nickel-EtOH-base [17-19], LiAlH 4 [10], NaBH 4 -TiCl 4 [20], and NaBH 4 -LiCl-Amberlyst [21]. Oxime ethers, nitriles, and azines were also reduced in the presence of Pd/C [19,22,23]. However, despite diversity of methods for the preparation of benzylamines, there are very limited published data on the synthesis of benzylamines with hydroxy and alkoxy groups in the aromatic ring [11,13,[16][17][18]21].In the present work we examined different synthetic approaches to functionally substituted benzylamines, primarily to those containing hydroxy and alkoxy substituents. In particular, such standard procedures as hydride reduction of aldehyde and ketone oximes with LiAlH 4 , reduction of ketone oximes with sodium in liquid ammonia, and reductive amination of ketones according to Leuckart-Wallach were studied.In the first step of our study we examined the possibility for synthesizing functionally substituted 1-phenylalkan-1-amines by reduction of the corresponding aromatic ketone oximes with LiAlH 4 ; as model substrates we used acetophenone oxime and its O-methyl ether. Both these substrates were completely reduced in boiling THF in 3 h, but the reactions were not selective: apart from the target 1-phenylethanamine, secondary N-ethylaniline was formed as a result of side Beckmann rearrangement followed by reduction of intermediate acetanilide. In the reaction with acetophenone oxime the ratio 1-phenylethanamine-N-ethylaniline was 1 : 1.5, and in the reduction of acetophenone O-methyloxime both products were formed in equimolar amounts. The reduction of acetophenone oxime with the system LiAlH 4 -Me 3 SiCl was more selective, and the ratio of 1-phenylethanamine and N-ethylaniline was 3 : 1. With a view to obtain functionally substituted benzylamine, 1-(4-hydroxyphenyl)ethanamine, the corresponding oxime was reduced with sodium in liquid ammonia. This reaction was not accompanied by side Beckmann rearrangement, and the target product was formed in high yield. As far as we known, we were the first to apply this procedure for the reduction of an aromatic ketone oxime having a hydroxy group in the aromatic ring. However, the use of sodium in liquid ammonia for the reduction of ketone oximes is strongly limited. For example, alkoxy-substitu...

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Comparison of different reducing systems in the synthesis of functionally substituted benzylamines from alkyl aryl ketones and aromatic aldehydes

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“…Condições reacionais para a oxidação de oximas para nitrocompostos Condições reacionais para a desidratação de oximas para nitrilas Aminas podem ser preparadas a partir da redução de cetoximas e aldoximas empregando-se vários agentes redutores, tais como: sódio metálico,44 LiAlH 4 , 110 NaH, formiato de amônio/Pd/C, formiato de amônio /magnésio,111 H 2 e Raney Nickel, 112 1,3,2-oxazaborolidinas, ésteres espiroboranos, 113 boranos (BH 3 •THF , 114 RuCl 2 (PPh 3 ), 115 NaBH 4 /TiCl 4 , 116 Esquema 23. Milios, C. J.; Stamatatos, T. C.; Perlepes, S. P. The coordination chemistry of pyridyl oximes.…”

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Oximes: Chemical Properties, Methods of Preparation and Applications in Synthesis of Nitrogen Functional Groups

Araújo

Gonsalves

2015

Revista Virtual De Química

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Oxime is an organic functional group having the following general formula RR'C=N-OH and although its unquestionable importance in the Coordination Chemistry and Organic Synthesis it is a subject underexplored by main chemistry textbooks in higher education adopted in Brazil. Thus, this article is a review about oximes organized in three parts. First are shown the properties of the oximes with emphasis in its isomerism and behavior in solution. After, are discussed some methods for obtaining oximes, such as oximation of carbonyl groups and double bonds, oxidation of amines, reduction of nitro compounds and the radical. Finally, in the third part of the article are treated some synthetic routes of nitrogen functional groups where oximes are precursors. ResumoOxima é u g upo fu io al o g i o ue ap ese ta a fó ula ge al RR'C=N-OH e apesar da sua relevância inquestionável na Química das Coordenações e na Síntese Orgânica este é um tema pouco explorado pelos principais livros de Química de ensino superior adotados no Brasil. Desta forma, o presente artigo trata de uma revisão sobre oximas, que está organizado em três partes. Inicialmente são mostradas as propriedades das oximas dando ênfase a sua isomeria e comportamento em solução. Em seguida, são abordadas algumas metodologias para a obtenção de oximas, como: oximação de carbonilas e duplas ligações, oxidação de aminas, redução de nitrocompostos e por via radicalar. Por fim, na terceira parte do artigo são tratadas algumas vias de síntese de grupos funcionais nitrogenados onde oximas são precursoras. Palavras-chave:Oxima; Propriedades Químicas das Oximas;

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“…In comparison with all other reduction process, catalytic transfer hydrogenation [17,18] and metal mediated reactions [19,20] are gaining more potential advantages due to their simple workup and selectivity. The utility of magnesium [21][22][23] as a powerful reducing agent in organic synthesis and in the field of catalytic transfer hydrogenation for the removal of commonly used protecting groups in peptide synthesis [24] and also for various functional group transformation is reported [25,26]. In our laboratory, the substituted nitroarenes are directly converted into azoarenes by employing the systems like HCOONH4/Pb [18], HCOONHEt3/Pb [27], HCOONHEt3/Mg [28], and CH3COONH4/Pb [29].…”

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Synthesis of azoarenes by reductive dimerization of nitroarenes using ammonium bromide and magnesium

Sridhara¹,

Suhas²,

Gowda³

2013

Eur. J. Chem.

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Magnesium‐Catalyzed Proficient Reduction of Oximes to Amines Using Ammonium Formate

Cited by 24 publications

References 24 publications

Comparison of different reducing systems in the synthesis of functionally substituted benzylamines from alkyl aryl ketones and aromatic aldehydes

Comparison of different reducing systems in the synthesis of functionally substituted benzylamines from alkyl aryl ketones and aromatic aldehydes

Oximes: Chemical Properties, Methods of Preparation and Applications in Synthesis of Nitrogen Functional Groups

Synthesis of azoarenes by reductive dimerization of nitroarenes using ammonium bromide and magnesium

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