Vapor-Phase Oxidation of Benzyl Alcohol Using Manganese Oxide Octahedral Molecular Sieves (OMS-2)

Vapor-phase selective oxidation of benzyl alcohol has been accomplished using cryptomelane-type manganese oxide octahedral molecular sieve (OMS-2) catalysts. A conversion of 92% and a selectivity to benzaldehyde of 99% were achieved using OMS-2. The role played by the oxidant in this system was probed by studying the reaction in the absence of oxidant. The natures of framework transformations occurring during the oxidation reaction were fully studied using temperature-programmed techniques, as well as in situ X-ray diffraction under different atmospheres

Oxidation of Alcohols and Activated Alkanes with Lewis Acid-Activated TEMPO

The reactivity of MCl3(η(1)-TEMPO) (M = Fe, 1; Al, 2; TEMPO = 2,2,6,6-tetramethylpiperidine-N-oxyl) with a variety of alcohols, including 3,4-dimethoxybenzyl alcohol, 1-phenyl-2-phenoxyethanol, and 1,2-diphenyl-2-methoxyethanol, was investigated using NMR spectroscopy and mass spectrometry. Complex 1 was effective in cleanly converting these substrates to the corresponding aldehyde or ketone. Complex 2 was also able to oxidize these substrates; however, in a few instances the products of overoxidation were also observed. Oxidation of activated alkanes, such as xanthene, by 1 or 2 suggests that the reactions proceed via an initial 1-electron concerted proton-electron transfer (CPET) event. Finally, reaction of TEMPO with FeBr3 in Et2O results in the formation of a mixture of FeBr3(η(1)-TEMPOH) (23) and [FeBr2(η(1)-TEMPOH)]2(μ-O) (24), via oxidation of the solvent, Et2O