Three novel, bifunctional triazine-based ligands, namely , and , containing both a TEMPO and a bipyridine moiety have been synthesized. These bpy/TEMPO-based molecules have been used as catalyst precursors for the copper-catalyzed aerobic oxidation of alcohols to aldehydes and ketones, in the presence of tert-BuOK as co-catalyst. The complexes obtained in situ from ligands and with copper(II) b...

Cytosolic sulfotransferases (SULT) catalyze the sulfation of structurally diverse drugs, endogenous compounds and xenobiotics. These reactions involve the transfer of a sulfuryl group from 3'-phosphoadenosine 5'-phosphosulfate (PAPS) to the hydroxyl/amino groups of acceptor molecules. Although sulfate conjugation is generally considered as a detoxication pathway producing more water-soluble and...

Halogenated aryl ketones (XC6H4COR: X ) Cl, F; R ) Me, Et, Ph) and benzyl alcohols (XC6H4CH(OH)R: X ) Cl; R ) Me, Et) have been reduced catalytically over Pt/C at 50 °C, by bubbling H2 at atmospheric pressure into a multiphase system consisting of a hydrocarbon solvent (isooctane) and an alkaline aqueous phase (KOH 50%) in the presence of a phase-transfer (PT) agent (onium salts or polyoxyethyl...

The first palladium-catalyzed enantioselective oxidation of secondary alcohols has been developed, utilizing the readily available diamine (-)-sparteine as a chiral ligand and molecular oxygen as the stoichiometric oxidant. Mechanistic insights regarding the role of the base and hydrogen-bond donors have resulted in several improvements to the original system. Namely, addition of cesium carbona...

A novel metallohost containing a substrate-binding site and two copper ions held by two bis-pyrazole ligand sets is described. The cavity of this molecule can bind dihydroxybenzene guests (association constants in chloroform are in the range K& = 2000-3000 M-1). In the presence of benzylic alcohols the Cu(II) centers of the metallohost are reduced to Cu(I). During this process the alcohols are ...

Mercaptobenzoic acid-palladium(0) complexes show high catalytic activity for S-benzylation with benzylic alcohols via the (η(3)-benzyl)palladium(II) cation in water. Notably, these palladium(0) complexes could play an important role in formation of active (η(3)-benzyl)palladium(II) cation complexes followed by S-benzylation. Hammett studies on the rate constants of S-benzylation by various subs...