“…Glycerol can be oxidized rapidly into DHA in the presence of cationic palladium catalyst and can result in more than 96% selectivity of DHA, with benzoquinone in acetonitrile solvent or oxygen as the terminal oxidant [80]. A previous study demonstrated the selective oxidation of glycerol to DHA in the presence of Pd-Ag catalyst [78]; as a result, 44% DHA is obtained under mild reaction conditions for 24 h of reaction time.…”
“…Glycerol can be oxidized rapidly into DHA in the presence of cationic palladium catalyst and can result in more than 96% selectivity of DHA, with benzoquinone in acetonitrile solvent or oxygen as the terminal oxidant [80]. A previous study demonstrated the selective oxidation of glycerol to DHA in the presence of Pd-Ag catalyst [78]; as a result, 44% DHA is obtained under mild reaction conditions for 24 h of reaction time.…”
“…The glycerol was oxidised to yield two molecules of CO 2 and one molecule of formic acid. In contrast, the selective oxidation of glycerol to dihydroxyacetone has been reported by Waymouth and co‐workers . The catalyst [Pd(OAc)(neocuproine)] 2 (OTf) 2 shows a remarkable selectivity for the oxidation of vicinal 1,2‐diols and polyols to the corresponding hydroxy ketones …”
A vanadium‐catalysed deoxydehydration (DODH) of neat glycerol has been developed. Cheap and readily available ammonium metavanadate (NH4VO3) affords higher yields of allyl alcohol than the well‐established catalyst methyltrioxorhenium. A study in which deuterium‐labelled glycerol was used was undertaken to further elucidate the dual role of glycerol as both an oxidant and reductant. This study led to the proposal of a metal‐catalysed DODH mechanism for the production of allyl alcohol and a deeper understanding of the formation of the byproducts acrolein and propanal.
“…[1] In this regard, palladiumcatalyzed oxidations of alcohols to carbonyl compounds have received significant attention in the past decade. [2] Elegant catalyst developments for this reaction include the combination of palladium(II) salts with heterocyclic Ndonor ligands [3] as well as carbene (NHC) ligands. [4] Notably, most of the known catalyst systems have been mainly applied to the oxidation of reactive benzylic alcohols.…”
Section: Introductionmentioning
confidence: 99%
“…Instead, reoxidation with molecular oxygen takes place, which is likely to proceed via the cyclic peroxy complex. [16] Investigations on the complexation of phosphine oxides, such as tri-n-butylphosphine oxide (L3), triphenylphosphine oxide ( 3 Cl] + complexes (see the Supporting Information). The 31 P NMR spectra of the different palladium complexes in CDCl 3 exhibit a broad signal, which is shifted downfield relative to the phosphorus signal of the free phosphine oxide ligand.…”
Section: Introductionmentioning
confidence: 99%
“…The BP86-computed OPPh 3 dissociation enthalpy of [Pd-A C H T U N G T R E N N U N G (O=PPh 3 ) 3 Cl] + is 32.3 kcal mol À1 . This energetic value is smaller than the first CO dissociation enthalpies of Fe(CO) 5 (42.8 kcal mol À1 from BP86 calculation [18] and (42 AE 2) kcal mol À1 from experiment [19] ), W(CO) 6 ((46 AE 2) kcal mol À1 [19] ), Cr(CO) 6 ((37 AE 2) kcal mol À1 [19] ), and Mo(CO) 6 ((40 AE 2) kcal mol À1 [19] ), but larger than that of [Co(CO) 5 ] + (16.7 kcal mol À1 from B3LYP calculation [20] and (18.1 AE 1.2) kcal mol À1 from experiment [21] ).…”
An efficient procedure for the oxidation of primary and secondary alcohols to aldehydes and ketones, respectively, with molecular oxygen under ambient conditions has been achieved. By applying catalytic amounts of Pd(OAc)2 in the presence of tertiary phosphine oxides (O=PR3) as ligands, a variety of substrates are selectively oxidized without formation of ester byproducts. Spectroscopic investigations and DFT calculations suggest stabilization of the active palladium(II) catalyst by phosphine oxide ligands.
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