Oxygen Atom Transfer from Peroxide Intermediates to Fullerenes

Charge effects on oxygen atom transfer.

The rhenium(V) complex [(HCpz3)ReOCl2]+ ([1]+), the tris(pyrazolyl)methane analogue of the known tris(pyrazolyl)borate complex (HBpz3)ReOCl2 (2), has been prepared. The two complexes are strikingly similar, as are the phosphine oxide adducts [(HCpz3)ReCl2(OPPh3)]Cl ([3]Cl) and (HBpz3)ReCl2(OPPh3) (4), which have been characterized by X-ray crystallography. Comparison of the bimolecular reductio...

Cu(ii)-catalyzed enantioselective oxygen atom transfer from oxaziridine to oxindole derivatives with chiral phenanthroline.

In the presence of a Cu(ii) complex of axially chiral, N,N,O-tridentate phenanthroline ligand (S)-2, asymmetric oxygen atom transfer of oxindole derivatives (3) using Davis' oxaziridine (4) occurred to give the corresponding 3-aryl-3-hydroxy-2-oxindole derivatives (1) with excellent enantioselectivity (up to 96% ee). The X-ray crystallographic analysis of the isolated Cu(ii) complex disclosed i...

Nonclassical oxygen atom transfer reactions of oxomolybdenum(VI) bis(catecholate).

Mechanistic studies indicate that the oxomolybdenum(vi) bis(3,5-di-tert-butylcatecholate) fragment deoxygenates pyridine-N-oxides in a reaction where the oxygen is delivered to molybdenum but the electrons for substrate reduction are drawn from the bound catecholate ligands, forming 3,5-di-tert-butyl-1,2-benzoquinone.

Driving force for oxygen-atom transfer by heme-thiolate enzymes.

The heme-thiolate peroxygenase from Agrocybe aegerita (AaeAPO, EC 1.11.2.1) is a versatile biocatalyst and cytochrome P450 analogue which catalyzes a variety of oxygenation reactions with high efficiency and selectivity. Our recent kinetic characterization of AaeAPO-catalyzed reactions has shown that AaeAPO compound I is an oxo-Fe porphyrin radical cation. The reactivity of AaeAPO-I toward a pa...

Oxygen Transfer from Blood to Mitochondria