15925-18-5Relevant articles and documents
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.
Primary amides to amines or nitriles: A dual role by a single catalyst
Das, Hari S.,Das, Shyamal,Dey, Kartick,Singh, Bhagat,Haridasan, Rahul,Das, Arpan,Ahmed, Jasimuddin,Mandal, Swadhin K.
supporting information, p. 11868 - 11871 (2019/10/11)
We report a manganese-catalyzed hydrosilylative reduction of various primary amides to amines (25 examples). On simple modification of the reaction conditions such as in the presence of a catalytic amount of secondary amide, the same catalyst can transform the primary amides into intermediate nitrile compounds (16 examples) in excellent yields. This is the first example where such a controlled catalytic transformation of primary amides to amines or nitriles with a single catalyst has been demonstrated.
Ru-Catalyzed Transfer Hydrogenation of Nitriles, Aromatics, Olefins, Alkynes and Esters
Alshakova, Iryna D.,Gabidullin, Bulat,Nikonov, Georgii I.
, p. 4860 - 4869 (2018/10/02)
This paper reports the preparation of new ruthenium(II) complexes supported by a pyrazole-phosphine ligand and their application to transfer hydrogenation of various substrates. These Ru complexes were found to be efficient catalysts for the reduction of nitriles and olefins. Heterocyclic compounds undergo transfer hydrogenation with good to moderate yields, affording examples of unusual hydrogenation of all-carbon-rings. Internal alkynes with bulky substituents show selective reduction to olefins with the unusual E–selectivity. Esters with strong electron-withdrawing groups can be reduced to the corresponding alcohols, if ethanol is used as the solvent. Possible mechanisms of hydrogenation and olefin isomerization are suggested on the basis of kinetic studies and labelling experiments.