Conversion of light alkanes to alkyl esters and chlorides using iodine oxides and chlorides: Radical versus non-radical pathways

Abstract

The selective and low temp. conversion of light alkanes to functionalized products has been a long-standing challenge. In protic media, the reaction of light alkanes (methane, ethane, propane) with iodine oxides results in the conversion to mono-functionalized products with alkyl trifluoroacetates as the primary products. The transformations are effective over a broad range of temps. (100 - 235 degrees C) and pressures (240-6900 kPa) in non-superacidic media. Alkane conversions between 15% and 40% with selectivity for mono-functionalized products between 85% and 95% have been achieved. The presentation will focus on mechanistic studies that incorporate selectivity patterns and kinetic isotope effects for conversion of light alkanes and model hydrocarbons (e.g., adamantane), spectroscopic identification of reaction intermediates, and computational modeling.