Selective Hydration of Nitriles to Amides Promoted by an Os–NHC Catalyst: Formation and X-ray Characterization of κ2-Amidate Intermediates
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Abstract
The complex [Os(η 6-p-cymene)(OH)IPr]OTf (1; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolylidene; OTf = CF 3SO 3) reacts with benzonitrile and acetonitrile to afford the κ 2-amidate derivatives [Os(η 6-p-cymene) {κ 2O,N-NHC(O)R}IPr]OTf (R = Ph (2), CH 3 (3)). Their formation has been investigated by DFT calculations (B3PWP1), starting from the model intermediate [Os(η 6-benzene)(OH)(CH 3CN)IMe] + (IMe = 1,3-bis(2,6-dimethylphenyl)imidazolylidene). Complex 2 has been characterized by X-ray diffraction analysis. In the presence of water, the κ 2-amidate species release the corresponding amides and regenerate 1. In agreement with this, complex 1 has been found to be an efficient catalyst for the selective hydration of a wide range of aromatic and aliphatic nitriles to amides, including substituted benzonitriles, cyanopyridines, acetonitrile, and 2-(4-isobutylphenyl)propionitrile among others. The mechanism of the catalysis is also discussed. © 2012 American Chemical Society.
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