ChemInform Abstract: Aerobic Oxidation Catalysis with Stable Radicals

Abstract

Aerobic Oxidation Catalysis with Stable Radicals -[141 refs.]. -(CAO, Q.; DORNAN, L. M.; ROGAN, L.; HUGHES, N. L.; MULDOON*, M. J.; Chem. Commun. (Cambridge) 50 (2014) 35, 4524-4543, http://dx.doi.org/10.1039/c3cc47081d ; Sch. Chem., Queen's Univ., Belfast BT9 5AG, UK; Eng.) -S. Adam 26-261

Iron(III) Nitrate/TEMPO-Catalyzed Aerobic Alcohol Oxidation: Distinguishing between Serial versus Integrated Redox Cooperativity

“…17−23 The mechanism of these reactions has not yet been characterized, but postulated pathways include both integrated and serial cooperativity. 5,17,[19][20][21]23 Stoichiometric alcohol oxidation reactions observed with FeCl 3 −TEMPO adducts are consistent with an "integrated" mechanism. 24−26 On the other hand, nearly all Fe/TEMPO catalysts use iron nitrates or include another NO x source that could contribute to a "serial" pathway.…”

Safe and Scalable Aerobic Oxidation by 2-Azaadamantan-2-ol (AZADOL)/NOx Catalysis: Large-Scale Preparation of Shi’s Catalyst

“…4 Among various methods for catalytic aerobic alcohol oxidation, methods catalyzed by nitroxyl radicals, such as 2,2,6,6tetramethylpiperidine-N-oxyl (TEMPO), have been extensively investigated (Figure 1). Two mechanistically distinct catalytic systems have been developed, 5 namely, (1) a nitroxyl radical with Cu cocatalysis featuring the generation of copper(II) alkoxide coupled with a redox cycle of nitroxyl radical−hydroxylamine 6 and (2) a nitroxyl radical with NO x cocatalysis featuring the generation of the corresponding oxoammonium salt. 7 Catalytic aerobic alcohol oxidation using a nitroxyl radical with Cu cocatalysis was first introduced by Semmelhack and co-workers in 1984.…”