Neutral, regioselective, copper-catalyzed hydration of some nitriles to amides

Ravindranathan, M.; Kalyanam, N.; Sivaram, Swaminathan

doi:10.1021/jo00145a052

Cited by 40 publications

(19 citation statements)

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“…The existence of an acetamide fragment in the reaction medium may possibly be explained in terms of copper-catalysed hydrolysis of acetonitrile. [33] Nitriles are compounds that are very stable under normal conditions and they are usually used as safe organic solvents. However, in recent years, the hydrolysis of nitriles to amides is a reaction that has attracted much attention.…”

Section: X-ray Diffraction Studiesmentioning

confidence: 99%

Metal‐Catalysed Oxidation Processes in Thiosemicarbazones: New Complexes with the Ligand N‐{2‐([4‐N‐Ethylthiosemicarbazone]methyl)phenyl}‐p‐toluenesulfonamide

Pedrido¹,

Romero²,

Bermejo³

et al. 2007

Chemistry A European J

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The coordination behaviour of a new thiosemicarbazone Schiff-base building block, N-{2-([4-N-ethylthiosemicarbazone]methyl)phenyl}-p-toluenesulfonamide, H2L1 (1), incorporating a bulky tosyl group, towards Mn II, Fe II, Co II, Ni II, Cu II, Zn II, Cd II, Ag I, Sn II, and Pb II has been investigated by means of an electrochemical preparative procedure. Most metal complexes of L1 have the general formula [M(L1)]2.nX (M=Mn, Fe, Co, Ni, Cu, Cd, Pb; n=0-4, X=H2O or CH3CN), as confirmed by the structure of [Pb(L1)]2 (15), in which the lone pair on lead is stereochemically active. This lead(II) complex shows an intense fluorescence emission with a quantum yield of 0.13. In the case of silver, the complex formed was found to possess a stoichiometry of [Ag2(L1)]2.3H2O. During reactions with manganese and copper metals, interesting catalysed processes have been found to take place, with remarkable consequences regarding the ligand skeleton structure. In synthesising the manganese complex, we obtained an unexpected dithiolate thiosemicarbazone tosyl ligand, H2L2, as a side-product, which has been fully characterised, including by X-ray diffraction analysis. In the case of copper, the solid complex has the formula [CuL1]2, but the crystallised product shows the copper atoms coordinated to a new cyclised thiosemicarbazone ligand, H2L3, as in the structures of the complexes [Cu(L3)]2.CH3CN (8) and [Cu(L3)(H2O)]2.CH3CN.H2O (9). The zinc complex [Zn(L1)]4 (12) displays a particular tetranuclear zeolite-type structure capable of hosting small molecules or ions, presumably through hydrogen bonding.

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Section: X-ray Diffraction Studiesmentioning

confidence: 99%

Metal‐Catalysed Oxidation Processes in Thiosemicarbazones: New Complexes with the Ligand N‐{2‐([4‐N‐Ethylthiosemicarbazone]methyl)phenyl}‐p‐toluenesulfonamide

Pedrido¹,

Romero²,

Bermejo³

et al. 2007

Chemistry A European J

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“…For nitrile hydration, many heterogeneous catalyst systems that involve transition metals (Mn,10 Cu,11 Ni,12 Ru,13 and Ag14) are known. Catalysts that contain supported Mg, Al, and Ga15a have also been reported.…”

Section: Methodsmentioning

confidence: 99%

Ein Original von der Münchner Museumsinsel: Otto Krätz

2008

Nachr Chem

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Going round again: Catalytic selective hydration of nitriles to amides by a safe and recyclable catalyst, Nafion‐Ru, is described. The reaction is general, inexpensive, conveniently carried out in water as solvent, and is applicable to diverse benzonitriles and heteroaromatic nitriles. Easy preparation of the catalyst and separation of the product, as well as simple regeneration and recycling of the catalyst are the salient features of this method.

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“…12, right) and [Cu(L105)(H 2 O)] 2 ·CH 3 CN·H 2 O are dinuclear species with two dianionic tetradentate bridging ligands [146]. In this case, the formation of a triazole ring in the new ligand was proposed to start with a nucleophilic attack of a thioamide nitrogen to the imine carbon, followed by the addition of an acetamide moiety (possibly the result of the copper catalyzed hydrolysis of acetonitrile) [335] and the formation of a new N-S bond which is attributable to the coordination of the metal followed by a reductive elimination [336]. [305].…”

Section: Scheme 16mentioning

confidence: 99%