The Hydration of Nitriles Catalyzed by the Combination of Palladium Nanoparticles and Copper Compounds

Ishizuka, Akinori; Nakazaki, Yoshiaki; Oshiki, Toshiyuki

doi:10.1246/cl.2009.360

Cited by 27 publications

(9 citation statements)

References 23 publications

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“…To circumvent all these limitations, several protocols using enzymes, , heterogeneous catalysts, and transition-metal complexes have been developed. In particular, a large variety of homogeneous catalysts highly selective toward amide formation have been described, with Murahashi’s ruthenium dihydride [RuH 2 (PPh 3 ) 4 ], Parkins’s platinum hydride [PtH(PMe 2 OH){(PMe 2 O) 2 H}], the acetylacetonate complex cis -[Ru(acac) 2 (PPh 2 py) 2 ], and the Rh(I)-based system [{Rh(μ-OMe)(cod)} 2 ]/PCy 3 (cod = 1,5-cyclooctadiene), showing remarkable activities under mild conditions.…”

Section: Introductionmentioning

confidence: 99%

Arene−Ruthenium(II) Complexes Containing Amino−Phosphine Ligands as Catalysts for Nitrile Hydration Reactions

et al. 2010

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Three different series of novel mononuclear arene-ruthenium(II) complexes containing aminophosphine ligands, namely, [RuCl 2 {κ 1 (P)-2-Ph 2 PC 6 H 4 CH 2 NHR}(η 6 -arene)], [RuCl 2 {κ 1 (P)-3-Ph 2 -PC 6 H 4 CH 2 NHR}(η 6 -arene)], and [RuCl 2 {κ 1 (P)-4-Ph 2 PC 6 H 4 CH 2 NHR}(η 6 -arene)] (arene = C 6 H 6 , p-cymene, 1,3,5-C 6 H 3 Me 3 , C 6 Me 6 ; R = i Pr, t Bu; all combinations), have been synthesized and fully characterized. These readily accessible species are efficient catalysts for the selective hydration of organonitriles into amides under challenging reaction conditions, i.e., pure aqueous medium in the absence of any cocatalyst, being much more active than their corresponding nonfunctionalized triphenylphosphine counterparts [RuCl 2 (PPh 3 )(η 6 -arene)]. The results obtained in this study indicate that the (amino-phosphine)ruthenium(II) complexes operate through a "bifunctional catalysis" mechanism in which the ruthenium center acts as a Lewis acid, activating the nitrile molecule, and the P-donor ligand acts as a Brønsted base, the pendant amino group generating the real nucleophile of the hydration process, i.e., the OHgroup.

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Section: Introductionmentioning

confidence: 99%

Arene−Ruthenium(II) Complexes Containing Amino−Phosphine Ligands as Catalysts for Nitrile Hydration Reactions

et al. 2010

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“…16,40 Addition of 1 mmol (100 mol%, 0.33 M) NaCl to the hydration of benzonitrile resulted in a slight decrease in conversion from 99 to 93% after 7 h. 41 This is in contrast to a Pd nanoparticle system in which addition of 5 mol% chloride ion (0.02 M) reduces nitrile hydration conversion from 87 to 2.7%. 42 Further evidence for the robust nature of the catalyst was obtained upon storing an aqueous solution of [RuCl 2 (PTA) 4 ] under air for four weeks at~0 • C. Hydration of benzonitrile performed using the stored aqueous solution of [RuCl 2 (PTA) 4 ] (1 mol% loading) resulted in a 83% conversion after 7 h compared to 87% by freshly-prepared catalyst in water; both reactions reached >99% conversion by 24 h.…”

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confidence: 96%

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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“…It is well known that with substrates containing nitrile group, the hydrolysis of the nitrile group could take place during the coupling reaction, producing the corresponding amide as byproduct. 59 However, the Suzuki reaction to obtain the desired biaryl product 3d with the PdNPs 8 nm in aqueous medium was successfully carried out. The only side product observed in a signicant amount was the one arriving from the dehalogenation of the substrates (15% of p-benzonitrile).…”

Section: Catalytic Performance Of Pvp-pdnps On the Suzuki Coupling Re...mentioning

confidence: 99%

Electrochemical synthesis of palladium nanoparticles in PVP solutions and their catalytic activity in Suzuki and Heck reactions in aqueous medium

et al. 2014

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The Hydration of Nitriles Catalyzed by the Combination of Palladium Nanoparticles and Copper Compounds

Cited by 27 publications

References 23 publications

Arene−Ruthenium(II) Complexes Containing Amino−Phosphine Ligands as Catalysts for Nitrile Hydration Reactions

Arene−Ruthenium(II) Complexes Containing Amino−Phosphine Ligands as Catalysts for Nitrile Hydration Reactions

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

Electrochemical synthesis of palladium nanoparticles in PVP solutions and their catalytic activity in Suzuki and Heck reactions in aqueous medium

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