140401-58-7Relevant academic research and scientific papers
Base-Catalyzed Hydrosilylation of Nitriles to Amines and Esters to Alcohols
Clarke, Joshua A.,Nikonov, Georgii I.,van der Est, Art
supporting information, p. 4434 - 4439 (2021/08/30)
Base-catalyzed hydrosilylation of nitriles to amines and esters to silylated alcohols is reported. This protocol tolerates electron-rich and electron-neutral olefins and works in the presence of basic functional groups (e. g. tertiary amines) but fails for acidic substrates, such as phenols and NH anilines. This catalytic system does not tolerate carbonyl groups, such as aldehydes, ketones, esters and carbamides, which are reduced to corresponding alcohols and amines. With the exact amount of silane, esters can be selectively reduced in the presence of nitriles, but the selectivity drops for the pairs ester/carboxamide and carboxamide/nitrile. Through competition experiments, the following preference in functional group reactivity was determined: ester > carboxamide > nitrile.
Synthesis of Molybdenum Pincer Complexes and Their Application in the Catalytic Hydrogenation of Nitriles
Leischner, Thomas,Spannenberg, Anke,Junge, Kathrin,Beller, Matthias
, p. 4543 - 4549 (2020/07/13)
A series of molybdenum(0), (I) and (II) complexes ligated by different PNP and NNN pincer ligands were synthesized and structurally characterized. Along with previously described Mo?PNP complexes Mo-1 and Mo-2, all prepared compounds were tested in the catalytic hydrogenation of aromatic nitriles to primary amines. Among the applied catalysts, Mo-1 is particularly well suited for the hydrogenation of electron-rich benzonitriles. Additionally, two aliphatic nitriles were transformed into the desired products in 80 and 86 percent, respectively. Moreover, catalytic intermediate Mo-1a was isolated and its role in the catalytic cycle was subsequently demonstrated.
Substituent effects. 14. Anomalous dissociation constants in water-organic solvent mixtures: benzylammonium ions and related systems
Hoefnagel, A. J.,Vos, R. H. de,Wepster, B. M.
, p. 22 - 28 (2007/10/02)
Thermodynamic dissociation constants in various water-organic solvent mixtures are given for benzylammonium, benzyldialkylammonium, and (2-phenylethyl)ammonium ions.Deviations from the Hammett equation (Eqn. 1) are similar to those observed for carboxylic acids, but of opposite sign.The extended Hammett equation (Eqn. 3), containing the hydrophobic constant, ?, yields good correlations.Derived secondary normal sigma values are exemplified.
