Allylic aldehydes are important fine and agrochemical intermediates, which find application in pesticides, fragrances and food additives. Their commercial synthesis often utilises toxic or hazardous stoichiometric oxidants such as chromates, permanganates or peroxides, and produces large quantities of waste.1 Heterogeneous catalysts can circumvent these problems, enabling the use of air or oxygen as benign oxidants, thereby offering alternative, atom-economical aerobic selective oxidation (selox) routes.2 Experimental single crystal3,4 and practical nanocatalyst5 studies reveal a positive synergistic interaction between Au and O in the gold/palladium-catalysed selox of crotyl alcohol to crotonaldehyde (a precursor to the food preservative sorbic acid). However, the underlying mechanism of this promotion, and impact of oxygen upon the chemistry of crotyl alcohol adsorption, C-H versus O-H activation, and competing crotonaldehyde decarbonylation pathways over gold, remains unknown. Here we present the results of quantum-chemical modelling that explore the reaction mechanism and the effect of co-adsorbed O2 over Au nanoparticles. 1. R. A. Sheldon, I. Arends, A. Dijksman, Catal. Today 2000 , 57, 157;  R. A. Sheldon, I. Arends, U. Hanefeld in Green chemistry and Catalysis, Wiley-VCH, Weinheim, 2007 , 133. 2. C. P. Vinod, K. Wilson, A. F. Lee, J. Chem. Tech. Biotech. 2011 , 86, 161.3. A.F. Lee, S.F.J. Hackett, G.J. Hutchings, S. Lizzit, J. Naughton, K. Wilson, Catal. Today 2009 , 145, 251.4. J. Naughton, A.F. Lee, S. Thompson, C.P. Vinod, K. Wilson, PCCP2010 ,12, 2670.5. A.F. Lee, C.V. Ellis, K. Wilson, N.S. Hondow, Catal. Today 2010 , 157, 243.

Mechanistic studies of the selective oxidation of crotyl alcohol to crotonaldehyde on bare and oxidised gold nanoparticles

247th National Meeting (2014)

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