A selective, efficient and environmentally friendly method for the oxidative cleavage of glycols

Abstract

An efficient and eco-friendly oxidative cleavage of glycols using DMSO as an oxidant catalyzed by dioxomolybdenum(vi) complexes has been developed.

Molybdenum‐Catalyzed Deoxygenation of Heteroaromatic N‐Oxides and Hydroxides using Pinacol as Reducing Agent

“…This way, the catalyst MoO 2 Cl 2 (L) 2 first would react with pinacol likely giving rise to a pinacolate complex such as A and releasing a molecule of water. The pinacolate ligand could then be oxidatively cleaved by the Mo(VI) center leading to a new oxomolybdenum(IV) species B . Immediate displacement of the weakly coordinated acetone by the corresponding N ‐oxide derivative D , which possesses an stronger coordination ability for the metal center, would afford a new complex C .…”

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

“…Beside the intrinsic problem related to the use of stoichiometric amounts of oxidants, most of these reagents suffer from severe drawbacks in terms of selectivity, toxicity, storage, handling, cost and solubility. More recently, catalytic procedures have been reported using homogeneous iron, molybdenum, copper, manganese, ruthenium, cobalt, palladium, or polyoxometalate complexes. Sacrificial stoichiometric organic or inorganic oxidants are however still required ,,.…”

“…More recently, catalytic procedures have been reported using homogeneous iron, molybdenum, copper, manganese, ruthenium, cobalt, palladium, or polyoxometalate complexes. Sacrificial stoichiometric organic or inorganic oxidants are however still required ,,. When O 2 is used as primary oxidant, high pressures, or activating sacrificial substrates,, are required or the scope of the substrate is limited to the more reactive tertiary or benzylic glycols .…”

New Motifs in Deoxydehydration: Beyond the Realms of Rhenium

“…Pinacol has been used as a reductant for the molybdenum‐catalysed deoxygenation of sulfoxides . Moreover, using DMSO as the oxidant, the oxidative cleavage of diols catalysed by MoO 2 Cl 2 (DMSO) 2 has been reported by Sanz and co‐workers . Further research into the molybdenum‐catalysed DODH reaction lead to the discovery that i PrOH could be used as both the reductant and solvent .…”

“…[21] Moreover,u sing DMSO as the oxidant, the oxidative cleavage of diols catalysed by MoO 2 Cl 2 (DMSO) 2 has been reported by Sanz and co-workers. [62] Further research into the molybdenum-catalysed DODH reactionl ead to the discovery that iPrOH could be used as both the reductant and solvent. [47] Substituting an alkane as the solvent with iPrOH increased both the yield and selectivity of the reaction.…”