Catalytic hydrogenation of nitriles and dehydrogenation of amines with the rhodium(<scp>I</scp>) hydrido compounds [RhH(PPri3)3] and [Rh2H2(µ-N2){P(cyclohexyl)3}4]

Yoshida, Tomohiro; Okano, Tamon; Otsuka, Sei

doi:10.1039/c39790000870

Cited by 89 publications

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“…Before our work, the homogeneously catalyzed hydrogenation of nitriles had only scarcely been investigated, as compared to C=C-N, C=N, and NO 2 reductions. [39][40][41][42][43][44][45][46][47][48][49] As shown in Scheme 1, a general problem in the catalytic hydrogenation of nitriles is the formation of secondary amines. This unwanted sidereaction is caused by the nucleophilic attack of the initially formed primary amine 3 on the imine intermediate 2.…”

Section: Resultsmentioning

confidence: 99%

Selective Catalytic Reductions of Amides and Nitriles to Amines

et al. 2010

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Section: Resultsmentioning

confidence: 99%

Selective Catalytic Reductions of Amides and Nitriles to Amines

et al. 2010

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“…It is worth noting that at lower catalyst loading (0.125 mol %), full conversion and excellent yield (> 99 %) are obtained within 10 min, albeit at higher temperatures (120-140 8C; Table 2, entries 8,9). The highest TOF (5783 h À1 ) observed for this reaction to date was obtained at 140 8C with 0.06 mol % catalyst loading (Table 2, entry 10).…”

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confidence: 80%

“…[6] More specifically, homogeneous reductions in the presence of few ruthenium, [7] rhodium, [8] and iridium [9] complexes are known. Notably, all these catalysts reveal the formation of significant amounts of side products, such as secondary amines and imines, which lower the selectivity and the overall yield of the desired primary amines.…”

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confidence: 99%

A General and Environmentally Benign Catalytic Reduction of Nitriles to Primary Amines

Enthaler

Addis

Junge

et al. 2008

Chemistry A European J

109

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Dedicated to Professor Günther Oehme on the occasion of his 70th birthdayA vast number of amines are produced by both the bulk and fine chemical industries, and a plethora of naturally occurring nitrogen compounds, such as alkaloids, amino acids, and nucleotides, play a pivotal role in biological processes. [1] During recent decades, several novel catalytic methods have been established for the synthesis of amines, such as palladium-catalyzed amination of aryl halides, [2] hydroaminations [3] and hydroaminomethylation of olefins or alkynes, [4] and homogeneous reductive aminations. [5] Nevertheless, the development of new and improved methods for the efficient and selective production of amines continues to be a challenging goal. Among the different known methods used, reductions are probably the most important due to the availability of starting materials (aldehydes, ketones, amides), price (hydrogen), and high atom efficiency. In this respect, the catalytic hydrogenation of nitriles also offers an interesting means of access to amines, which is used in industry for several products. In organic synthesis, nitriles are commonly reduced with stoichiometric amounts of metal hydrides, or in the presence of heterogeneous catalysts based on Pd, Ni, Co, etc. The former approach is expensive and not environmentally benign (over-stoichiometric amounts of waste), whereas the latter has limitations with respect to functional group tolerance and the excess of ammonia needed for high chemoselectivity. Surprisingly, the homoge-Herein, we describe for the first time the successful application of an easy-to-adopt catalytic system formed from commercially available [RuA C H T U N G T R E N N U N G (cod)methylallyl 2 ] (cod = 1,5-cyclooctadiene) and DPPF (1,1-bis(diphenylphosphino)ferrocene) for the homogeneous hydrogenation of a variety of aromatic and aliphatic nitriles, with excellent catalyst activity and high chemoselectivity. Scheme 1. Selectivity in the catalytic reduction of nitriles.

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“…[6] Until now, the homogeneous hydrogen- ation of nitriles to amines was realized based on Ru, [7] Ir, [8] Rh, [9] Re [10] and Mo. [11] Most of these catalytic systems make use of P-or P,N-ligands requiring the addition of base for catalyst activation and to prevent side reactions.…”

Section: Introductionmentioning

confidence: 99%

Hydrogenation of Aliphatic and Aromatic Nitriles Using a Defined Ruthenium PNP Pincer Catalyst

et al. 2015

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Catalytic hydrogenation of nitriles and dehydrogenation of amines with the rhodium(I) hydrido compounds [RhH(PPrⁱ₃)₃] and [Rh₂H₂(µ-N₂){P(cyclohexyl)₃}₄]

Cited by 89 publications

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Selective Catalytic Reductions of Amides and Nitriles to Amines

Selective Catalytic Reductions of Amides and Nitriles to Amines

A General and Environmentally Benign Catalytic Reduction of Nitriles to Primary Amines

Hydrogenation of Aliphatic and Aromatic Nitriles Using a Defined Ruthenium PNP Pincer Catalyst

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Catalytic hydrogenation of nitriles and dehydrogenation of amines with the rhodium(I) hydrido compounds [RhH(PPri3)3] and [Rh2H2(µ-N2){P(cyclohexyl)3}4]

Cited by 89 publications

References 0 publications

Selective Catalytic Reductions of Amides and Nitriles to Amines

Selective Catalytic Reductions of Amides and Nitriles to Amines

A General and Environmentally Benign Catalytic Reduction of Nitriles to Primary Amines

Hydrogenation of Aliphatic and Aromatic Nitriles Using a Defined Ruthenium PNP Pincer Catalyst

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Catalytic hydrogenation of nitriles and dehydrogenation of amines with the rhodium(I) hydrido compounds [RhH(PPrⁱ₃)₃] and [Rh₂H₂(µ-N₂){P(cyclohexyl)₃}₄]