His research interests are mainly concerned with the application of catalytic methods, in particular catalytic oxidations using homogeneous, heterogeneous and biocatalysts, in organic synthesis. He is the author/ editor of several books on the subject of catalysis, notably "Metal Catalyzed Oxidations of Organic Compounds" which he coauthored with Jay Kochi.
Three methods are described, in the context of the guiding principles of green chemistry, for the catalytic oxidation of alcohols. The first employs a recyclable oligomeric TEMPO catalyst (PIPO) and sodium hypochlorite as the oxidant in a bromide-free and chlorinated hydrocarbon solvent-free system. The second involves a ruthenium/TEMPO catalyst and oxygen as the oxidant. The third consists of a recyclable water-soluble palladium-diamine complex in conjunction with air as the oxidant in an aqueous biphasic system. The mechanisms of the ruthenium/TEMPO- and palladium-catalyzed oxidations are discussed, and the mechanism of the former is compared with that of the analogous copper/TEMPO catalyst.
Alcohol oxidations are typically performed with stoichiometric reagents that generate heavy-metal waste and are usually run in chlorinated solvents. A water-soluble palladium(II) bathophenanthroline complex is a stable recyclable catalyst for the selective aerobic oxidation of a wide range of alcohols to aldehydes, ketones, and carboxylic acids in a biphasic water-alcohol system. The use of water as a solvent and air as the oxidant makes the reaction interesting from both an economic and environmental point of view.
The combination of RuCl2(PPh3)3 and TEMPO affords an efficient catalytic system for the aerobic oxidation of a variety of primary and secondary alcohols, giving the corresponding aldehydes and ketones, in >99% selectivity in all cases. The Ru/TEMPO system displayed a preference for primary vs secondary alcohols. Results from Hammett correlation studies (rho = -0.58) and the primary kinetic isotope effect (kH/kD = 5.1) for the catalytic aerobic benzyl alcohol oxidations are inconsistent with either an oxoruthenium (O=Ru) or an oxoammonium based mechanism. We postulate a hydridometal mechanism, involving a "RuH2(PPh3)3" species as the active catalyst. TEMPO acts as a hydrogen transfer mediator and is either regenerated by oxygen, under catalytic aerobic conditions, or converted to TEMPH under stoichiometric anaerobic conditions.
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