Efficient Vanadium‐Catalyzed Aerobic C−C Bond Oxidative Cleavage of Vicinal Diols

Abstract

The aerobic oxidative CÀC bond cleavage of vicinal diols catalyzed by vanadium amino triphenolates is described. Our results show that CÀC bond cleavage can be performed in different solvents, under an air or oxygen atmosphere, with a large variety of glycols (cyclic or linear, with aromatic or aliphatic substituents) affording the corresponding carbonyl derivatives with high chemoselectivity.Reactions can be performed with as little as 10 ppm of catalyst reaching TON up to 81,000 and TOFs of up to 4150 h À1 . A reaction mechanism, rationalized by density functional theory calculations, is also proposed.

Aerobic oxidative cleavage of 1,2-diols catalyzed by atomic-scale cobalt-based heterogeneous catalyst

“…Although these catalytic systems are capable of cleaving simple diols with molecular oxygen, most of them are still suffering from drawbacks such as low product selectivity, limited substrate range, the use of expensive noble metals (e.g., Pd, Ru), the required harsh conditions, activating sacrificial substrates, and no reusability of the catalyst. Very recently, Giulia Licini and co-workers reported vanadium-catalyzed aerobic C-C bond oxidative cleavage of vicinal diols under relatively mild conditions (80-100°C) in different solvents, with a large variety of diols, affording the corresponding carbonyl derivatives 14 . Another recent example of mild silver(I)-catalyzed oxidative cleavage of 1,2-diols into carboxylic acids with wide adaptability was reported by Li and co-workers 15 .…”

One-pot synthesis of new alkyl 1-naphthoates bearing quinoline, pyranone and cyclohexenone moieties via metal-free sequential addition/oxidation reactions

“…31,37 The C-C bond oxidative cleavage of vicinal diols has been studied in many literatures. [38][39][40] Vicinal diols are cleaved by oxo-donor reagents such as periodic acid to yield carbonyl-containing derivatives via oxo-transfer mechanism, depending on the reaction conditions, reagents, and the number of groups substituted on the carbon atoms bearing the hydroxyl groups. In this study, no attempts were carried out for separation of diols intermediates 4, thus, aer the addition step, they directly treated with H 5 IO 6 as the oxidant reagent and the reaction was allowed to continue at room temperature.…”

Organic Polyradicals as Redox Mediators: Effect of Intramolecular Radical Interactions on Their Efficiency

“…In recent years, we reported about the use of tetradentate metal complexes in catalysis, − molecular recognition, − and as molecular scaffolds for multiple functionalization. Among the different structures, μ-oxo dinuclear titanium complex 1 represents the ideal architecture to become a scaffold for multiple functionalization (Scheme ).…”