Catalyst-Dependent Selective Hydrogenation of Nitriles: Selective Synthesis of Tertiary and Secondary Amines

Monguchi, Yasunari; Mizuno, Masahiro; Ichikawa, Tomohiro; Fujita, Yuki; Murakami, Eri; Hattori, Tomohiro; Maegawa, Tomohiro; Sawama, Yoshinari; Sajiki, Hironao

doi:10.1021/acs.joc.7b01823

Cited by 30 publications

(26 citation statements)

References 37 publications

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“…The lacko fs electivity for the primary amine in these hydrogenation reactions is well-known, [19] and product mixtures are often obtained.R elated to our observation of ar easonable degree of selectivity to the tertiaryp roduct, Monguchi, Sajiki and co-workers reported very recently that mild Pd/C-catalyzed hydrogenation of aliphatic nitrilesl eads to tertiary amines as the major product. [20] Compound 6b is obtained as am ixture of diastereoisomers, as can be seen from the NMR spectra:a lthought heir chemical shifts are close, the 13 CNMR spectra clearly show 3d istinct resonances for the RRR, RSS and RSR diastereomers (and their respective antipodes). The related tris(2-hydroxylalkyl)amines derived from ethylenea nd propylene oxide, [1a] have found extensive use (for example:m ain group atranes, [21] tripodall igands in coordination chemistry [22] and catalysis, [23] cosmetics additives [24] ).…”

Section: Resultsmentioning

confidence: 86%

Oxa‐Michael Addition to α,β‐Unsaturated Nitriles: An Expedient Route to γ‐Amino Alcohols and Derivatives

et al. 2018

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Water addition to α,β‐unsaturated nitriles would give facile access to the β‐hydroxy‐nitriles, which in turn can be hydrogenated to the γ‐amino alcohols. We have previously shown that alcohols readily add in 1,4‐fashion to these substrates using Milstein's Ru(PNN) pincer complex as catalyst. However, attempted water addition to α,β‐unsaturated nitriles gave the 3‐hydroxynitriles in mediocre yields. On the other hand, addition of benzyl alcohol proceeded in excellent yields for a variety of β‐substituted unsaturated nitriles. Subsequent treatment of the benzyl alcohol addition products with TMSCl/FeCl3 resulted in the formation of 3‐hydroxy‐alkylnitriles. The 3‐benzyloxy‐alkylnitriles obtained from oxa‐Michael addition also could be hydrogenated directly in the presence of acid to give the amino alcohols as their HCl salts in excellent yields. Hydrogenation under neutral conditions gave a mixture of the secondary and tertiary amines. Hydrogenation in the presence of base and Boc‐anhydride gave the orthogonally bis‐protected amino alcohols, in which the benzyl ether can subsequently be cleaved to yield Boc‐protected amino alcohols. Thus, a variety of molecular scaffolds with a 1,3‐relationship between O‐ and N‐functional group is accessible starting from oxa‐Michael addition of benzyl alcohol to α,β‐unsaturated nitriles.

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Section: Resultsmentioning

confidence: 86%

Oxa‐Michael Addition to α,β‐Unsaturated Nitriles: An Expedient Route to γ‐Amino Alcohols and Derivatives

et al. 2018

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“…A further heterogeneous catalyst being commonly used for metal-catalyzed hydrogenation is Pd/C. [7,8,[16][17][18] When operating under smooth reaction conditions such as 25°C as reaction temperature and 1-20 bar hydrogen pressure, a minimum amount of 1 mol% of the catalyst Pd/C was found to be needed for achieving a high conversion within a reaction time of 20 or 21 h ( Table 2). For example, >99% conversion was obtained at just 1 bar of hydrogen pressure and at a low reaction temperature of 25°C.…”

Section: Resultsmentioning

confidence: 99%

“…For example, when using Pd/C as a heterogeneous catalyst (being frequently used for various types of hydrogenation reactions), the tertiary amine is formed as a major product in the hydrogenation of aliphatic nitriles. [7,8] Also in case of the heterogeneous catalysts Ru/C [9] and Raney nickel, [10,11] insufficient selectivities toward the primary amine have been observed. Although some modifications of hydrogenation conditions and additives were found, which positively influence the selectivity of the Ni-catalyst for primary amines in the hydrogenation of nitriles, there is still a demand for general procedures to hydrogenate various nitriles and in particular aliphatic nitriles selectively to primary amines.…”

Section: Introductionmentioning

confidence: 99%

Selective Hydrogenation of Fatty Nitriles to Primary Fatty Amines: Catalyst Evaluation and Optimization Starting from Octanenitrile

Hinzmann

Gröger

2019

Euro J Lipid Sci & Tech

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In this contribution, an evaluation of the potential of various homogeneous and heterogeneous catalysts for a selective hydrogenation of fatty nitriles toward primary amines is reported exemplified for the conversion of octanenitrile into octane-1-amine as a model reaction. When using heterogeneous catalysts such as the ruthenium catalyst Ru/C, the palladium catalyst Pd/C, and the platinum catalyst Pt/Al 2 O 3 , low selectivities in the hydrogenation are observed, thus leading to a large portion of secondary and tertiary amine side-products. For example, when using Ru/C as a heterogeneous catalyst, high conversions of up to 99% are obtained but the selectivity remains low with a percentage of the primary amine being at 60% at the highest. The study further reveals a high potential of homogeneous ruthenium and manganese catalysts. When also taking into account economical considerations with respect to the metal price, in particular, manganese catalysts turn out to be attractive for the desired transformation and their application in the model reaction leads to the desired primary amine product with excellent conversion, selectivity, and high yield. Practical Applications: This work describes an optimized hydrogenation process for transforming fatty nitriles to their corresponding primary amines. In general, fatty amines belong to the most applied fatty acid-derived compounds in the chemical industry with an annual product volume exceeding 800 000 tons per year in 2011 and are widely required in the chemical industry since such compounds are either directly used in home products such as fabric softeners, dishwashing liquids, car wash detergents, or carpet cleaners or in a broad range of industrial products, for example, lubricating additives, flotation agents, dispersants, emulsifiers, corrosion inhibitors, fungicides, and bactericides, showing additional major applications, e.g., in the detergents industry. Among them primary amines play an important industrial role. However, a major concern of current processes is the lack of selectivity and the formation of secondary and tertiary amines as side-products. By modifying a recently developed catalytic system based on manganese as economically attractive and environmentally benign metal component an efficient and selective access to fatty amines when starting from the corresponding nitriles is achieved. For example, hydrogenation of octanenitrile leads to a synthesis of octane-1-amine with >99% conversion and excellent selectivity with formation of secondary and tertiary amine side-products being suppressed to an amount of <1%.

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“…Aromatic nitriles and cyclohexanecarbonitrile were converted to secondary amines, while aliphatic nitriles led to tertiary amines. Other impressive results were, most recently, obtained in cyclohexane as solvent and at 25–60°C under ambient hydrogen pressure . Pd/C catalyzed the selective hydrogenation of aliphatic nitriles to the corresponding tertiary amines, whereas Rh/C led to the selective formation of secondary amines.…”

Section: Introductionmentioning

confidence: 99%

“…Pd/C catalyzed the selective hydrogenation of aliphatic nitriles to the corresponding tertiary amines, whereas Rh/C led to the selective formation of secondary amines. Sterically hindered cyclohexanecarbonitrile gave selectively secondary amines in the presence of either Pd/C or Rh/C . Finally Pt nanowires have been used as a catalyst for the selective hydrogenation of nitriles to symmetric secondary amines, under a hydrogen pressure of 1–4 bar …”

Section: Introductionmentioning

confidence: 99%

Chemoselective hydrogenation of nitriles to secondary or tertiary amines catalyzed by aqueous‐phase catalysts supported on hexagonal mesoporous silica

Ajjou

Robichaud

2018

Applied Organom Chemis

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The first supported aqueous-phase catalyst for the hydrogenation of nitriles is revealed. The catalyst prepared from Pd(PhCN) 2 Cl 2 , water-soluble ligand 2,2′-biquinoline-4,4′-dicarboxylic acid dipotassium salt and mesoporous silica is a highly efficient catalyst for the selective formation of secondary or tertiary amines from aromatic or aliphatic nitriles. The catalytic system is stable and can be recycled and reused three times without loss of activity and selectivity.This environmentally friendly process is, in addition, an attractive alternative to many homogeneous and heterogeneous catalysts because of its easy preparation and the moderate operational conditions under which it is highly active.

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Catalyst-Dependent Selective Hydrogenation of Nitriles: Selective Synthesis of Tertiary and Secondary Amines

Cited by 30 publications

References 37 publications

Oxa‐Michael Addition to α,β‐Unsaturated Nitriles: An Expedient Route to γ‐Amino Alcohols and Derivatives

Oxa‐Michael Addition to α,β‐Unsaturated Nitriles: An Expedient Route to γ‐Amino Alcohols and Derivatives

Selective Hydrogenation of Fatty Nitriles to Primary Fatty Amines: Catalyst Evaluation and Optimization Starting from Octanenitrile

Chemoselective hydrogenation of nitriles to secondary or tertiary amines catalyzed by aqueous‐phase catalysts supported on hexagonal mesoporous silica

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