Flavin-Catalyzed Oxygen Atom Insertion into Rhenium-Methyl Produces Methanol

1. Flavin-Catalyzed Oxygen Atom Insertion into Rhenium-Methyl Produces Methanol Scientific Achievement Flavin organocatalysts demonstrated activity for oxygen atom insertion into a rhenium—methyl bond to ultimately produce methanol with rate enhancements up to 600-fold. • Research Details • - Insertion of an oxygen atom into a metal—carbon bond is one of three key steps in the catalytic cycle for partial oxidation of methane to methanol. • Three organocatalysts, based on flavin compounds, were demonstrated to enhance the rate of methanol production from the reaction of methylrhenium trioxide with hydrogen peroxide. • Density functional theory calculations predicted the efficacy of the flavin-based catalysts, which are small molecule mimics of more complex enyzmes. Work was performed at the University of Virginia, Princeton University and the University of North Texas. M. Pouy, E. Milczek, T. Figg, B. Otten, B. Prince, T. Gunnoe, T. Cundari, J. Groves, J. Am. Chem. Soc. 2012, 134, 12920-12923 doi 10.1021/ja3054139 Significance and Impact Metal-catalyzed C-O bond formation is a key step in upgrading of fossil resources, especially conversion of natural gas to liquid fuel. The reported flavin catalysts provide proof-of-concept for a new approach for oxygen- functionalization of methyl ligands.