Unprecedented synthesis of symmetrical azines from alcohols and hydrazine hydrate using nickel based NNN-pincer catalyst: An experimental and computational study

Hydrazine as Facile Nitrogen Source for Direct Synthesis of Amines over a Supported Pt Catalyst

“…Based on the above results for mechanistic studies and literature reports, ,− a tentative mechanism for this N 2 H 4 -involved direct transformation of alcohols to secondary amines was proposed in Scheme . Initially, the Pt/TiO 2 -A-catalyzed dehydrogenation of primary alcohol 1 forms the corresponding aldehyde 11 , which is trapped by the condensation of hydrazine hydrate 2 to give the coupling adduct azine 5 .…”

“…In recent years, hydrazine has attracted much attention as a novel nitrogen source in organic synthesis and catalysis. ,− As an unstable but more reactive amine, hydrazine could be used in straightforward approaches to prepare nitrogen-containing products, if the catalytic system is just right. Recently, significant progresses have been made to apply hydrazine in the synthesis of azines, − N-substituted hydrazones, or anilines , (Scheme a).…”

“…In recent years, hydrazine has attracted much attention as a novel nitrogen source in organic synthesis and catalysis. ,− As an unstable but more reactive amine, hydrazine could be used in straightforward approaches to prepare nitrogen-containing products, if the catalytic system is just right. Recently, significant progresses have been made to apply hydrazine in the synthesis of azines, − N-substituted hydrazones, or anilines , (Scheme a). Very recently, Li and co-workers further achieved the direct synthesis of primary anilines or secondary arylamines from phenols and hydrazine with careful modulation of the Pd catalytic system with a base and additives (Scheme a), in which phenols were temporarily reduced to cyclohexanone derivatives to react with hydrazine.…”

Non-Pincer-Type Arene Ru(II) Catalysts for the Direct Synthesis of Azines from Alcohols and Hydrazine under Aerobic Conditions

“…Recently, the groups of Milstein 18 and Gunanathan 19 reported the utilisation of ruthenium-PNP pincer complexes as catalyst for the direct synthesis of symmetrical azines from alcohols and hydrazine hydrate. Similarly, the groups of Goswami 20 and Shiekh 21 developed nickel pincer catalysts. To the best of our knowledge, there is no there is no example of catalyst achieving the direct synthesis of symmetrical azines using non-pincer type complexes.…”

Mechanism of atom economical conversion of alcohols and amines to amides using Fe(ii) pincer catalyst. An outer-sphere metal–ligand pathway or an inner-sphere elimination pathway?

“…Furthermore, the complete understanding of the reaction mechanism and the energetics of the reaction pathways will be advantageous to the researchers for the development and design of new catalysts. Being interested in catalyst designing and understanding their mechanistic aspects, 29 our aim in the present work is to elucidate the underlying mechanism of the catalytic reaction and to study the effects of various ligand modications on the catalytic activity of the catalyst using state-of-the-art density functional methodologies.…”