Sustainability, in essence the development of methodologies to meet the needs of the present without compromising those of future generations, has become a watchword for modern society, with governmental and multinational corporations promoting international research programmes into sustainable food, energy and materials. The selective oxidation (selox) of alcohols, carbohydrates and related a,�-unsaturated substrates represent an important class of reactions that underpin the synthesis of valuable chemical intermediates [1]. Heterogeneous catalysts utilising oxygen or air offer vastly improved activity, selectivity and overall atom efficiency in alcohol selox, but are particularly demanding due to the requirement to activate molecular oxygen and C-O bonds in close proximity at a surface in a solid-liquid-gas environment, and must also be scalable in terms of catalyst synthesis and implementation.Significant advances have been made in understanding the fundamental mode of action of heterogeneous palladium catalysts towards aerobic alcohol selox through the application of in-situ and operando spectroscopies, and parallel improvements in inorganic synthetic protocols offering tunable metal nanoparticles and support architectures. Here we show how identification of the active catalytic species via in-situ XPS and operando liquid and vapour XAS studies, and the development of highly ordered (and hierarchical) nanoporous supports [2], enables optimisation of this structure-sensitive chemistry, resulting in striking rate and selectivity enhancements for selox of diverse allylic alcohols including challenging sesquiterpenoids.[1] J.Chem.Tech.Biotech. 2011, 86, 161-171.[2] ACS Catal. 2013, 3, 2122-2129.

Rational design of heterogeneous catalysts for the selective aerobic oxidation of alcohols

248th National Meeting (2014)

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