2-Diphenylphosphanyl-4-pyridyl(dimethyl)amine as an effective ligand for the ruthenium(II) complex catalyzed homogeneous hydration of nitriles under neutral conditions

Muranaka, Makoto; Hyodo, Isao; Okumura, Wataru; Oshiki, Toshiyuki

doi:10.1016/j.cattod.2010.11.050

Cited by 38 publications

(14 citation statements)

References 52 publications

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“…This is in agreement with results for other catalyst systems although there have been exceptions reported . As previously reported, ortho ‐substituted benzonitriles exhibit lower conversion relative to meta ‐ and para ‐substituted benzonitriles (entries 2–4, 6–9, 14–16), which is attributed to steric hindrance of the ortho ‐substituted benzonitriles. The conversion proceeds smoothly even in the presence of heteroatoms such as N, O and S in the substrates (entries 17–23) and a range of heterocyclic aromatic amides are obtained in excellent isolated yields.…”

Section: Resultssupporting

confidence: 92%

Polymer‐anchored Ru(II) complex as an efficient catalyst for the synthesis of primary amides from nitriles and of secondary amides from alcohols and amines

Ghosh

Roy

Molla

2014

Applied Organom Chemis

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A polymer-anchored ruthenium(II) catalyst was synthesized and characterized. Its catalytic activity was evaluated for the preparation of primary amides from aqueous hydration of nitriles in neutral condition. A range of nitriles were successfully converted to their corresponding amides in good to excellent yields. The catalyst was also effective in the preparation of secondary amides from the coupling of alcohols and amines. The catalyst can be facilely recovered and reused six times without a significant decrease in its activity.

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Section: Resultssupporting

confidence: 92%

Polymer‐anchored Ru(II) complex as an efficient catalyst for the synthesis of primary amides from nitriles and of secondary amides from alcohols and amines

Ghosh

Roy

Molla

2014

Applied Organom Chemis

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“…3; 2-3 equiv. per Ru), Oshiki and co-workers were able to perform the selective hydration of a variety of organonitriles in DME at 80 ºC [24]. However, the TOF values reached were only modest (up to 5 h -1 ) and incomplete conversions were in some cases observed.…”

Section: Homogeneous Ruthenium-based Catalystsmentioning

confidence: 99%

Metal-catalyzed nitrile hydration reactions: The specific contribution of ruthenium

Garcı́a-Álvarez

Francos

Tomás‐Mendivil

et al. 2014

Journal of Organometallic Chemistry

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The hydration of nitriles is an atom economical route to generate primary amides of great academic and industrial significance. From an academic perspective, considerable progress has been made toward the development of transition metal catalysts able to promote this hydration process under mild conditions. In this context, with regard to activity, selectivity, functional group compatibility and modes of reactivity, the most versatile nitrile hydration catalysts discovered to date are based on ruthenium complexes. Herein, a comprehensive account of the different homogeneous ruthenium catalysts described in the literature is presented. Heterogeneous ruthenium-based systems are also discussed.

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“…9-12, [16][17][18] Recently, Cadierno and co-workers reported a series of Ru(II) and Ru(IV) complexes with nitrogen-containing phosphines for nitrile hydration in water. 9-12, 27 The superior activity of [RuCl 2 (h 6 -benzene)(PTA)], where PTA = 1,3,5-triaza-7-phosphaadamantane, over [RuCl 2 (h 6 -benzene)(PPh 3 )], was attributed to the cooperative effect of the PTA amine functionality activating water via hydrogen bonding.…”

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confidence: 99%

“…(18) c 99 (53) 99 (67) 99 (55) 99 (61) 99 (52) 99 (66) 99 (69) 99 (80) 99 (92) 96 (85) 95 (89) 85 (87)…”

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Aqueous and biphasic nitrile hydration catalyzed by a recyclable Ru(ii) complex under atmospheric conditions

Lee

Frost

2012

Green Chem.

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RuCl 2 (PTA) 4 ] (PTA = 1,3,5-triaza-7-phosphaadamantane) was found to be a highly active catalyst for aqueous phase nitrile hydration at 100 • C in air. Near quantitative conversion of aromatic, alkyl, and vinyl nitriles to their corresponding amides was observed. The reaction tolerated ether, hydroxyl, nitro, bromo, formyl, pyridyl, benzyl, alkyl, and olefinic functional groups. Some amides were isolated by simple decantation from the aqueous phase catalyst. Catalyst loading down to 0.001 mol% was examined with turnover numbers as high as 22 000 observed. The catalyst was stable for weeks in solution and could be reused more than five times without significant loss of activity.Amides are versatile and important synthetic intermediates used in the production of a variety of plastics, detergents, lubricants, and polymers. 1,2 Traditional methods of hydrating nitriles to amides involve the use of strong bases or acids under harsh conditions, often inducing undesired hydrolysis to carboxylic acids. 1-5 During neutralization salt formation can lead to contamination, separation, and pollution problems. 1-3 Moreover, poor tolerance for sensitive functional groups is often observed under such conditions. 1-3 A variety of transition metal complexes have been developed as efficient catalysts for nitrile hydration in organic media often with air-sensitive or non-recyclable catalysts. 1-7 Water, with its unique properties, has seen increased use as a solvent in stoichiometric and catalytic reactions. 8 Recently several aqueous homogeneous 9-11 and heterogeneous 12-15 nitrile hydration reactions have been reported under inert atmosphere.One common mechanistic pathway proposed for the hydration of nitriles involves nitrile coordination to a metal followed by nucleophilic attack by water on the nitrile carbon. 1 Recent studies have shown that nucleophilic attack can be promoted by activating water via hydrogen bonding to a functionalized ligand. 9-12,16-18 † Electronic supplementary information (ESI) available: Experimental details including nitrile hydration and catalyst recycling procedures, 31 P{ 1 H} NMR spectrum of the reaction mixture, and GC chromatogram, 1 H and 13 C{ 1 H} NMR spectra of isolated amides. See

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2-Diphenylphosphanyl-4-pyridyl(dimethyl)amine as an effective ligand for the ruthenium(II) complex catalyzed homogeneous hydration of nitriles under neutral conditions

Cited by 38 publications

References 52 publications

Polymer‐anchored Ru(II) complex as an efficient catalyst for the synthesis of primary amides from nitriles and of secondary amides from alcohols and amines

Polymer‐anchored Ru(II) complex as an efficient catalyst for the synthesis of primary amides from nitriles and of secondary amides from alcohols and amines

Metal-catalyzed nitrile hydration reactions: The specific contribution of ruthenium

Aqueous and biphasic nitrile hydration catalyzed by a recyclable Ru(ii) complex under atmospheric conditions

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