​There is a growing interest in alkylfurans as potential biofuels. Recent work has highlighted the need for further study of the atmospheric oxidation mechanism of 2-methylfuran (2MF). This study utilizes the high level composite computational methods, G4 and CBS-QB3, to determine the bond dissociation energies for the C–H bond in 2MF and the reaction enthalpies and barrier heights of several of the known possible initiation reaction pathways. This study also investigates the possible subsequent low temperature reaction pathways following the addition of OH and then O2 onto the 2MF ring. The placement of the OH and O2 on the ring, either cis or trans to each other, dictates the viability of subsequent reactions. Of particular interest is the observation that 1,4 H-migrations that abstract the hydrogen bound to the same carbon as the OH have abnormally low barrier height. This dramatic decrease puts the reaction barrier lower than concerted eliminations and 6-membered ring Waddington-type reactions. In addition, a novel reaction type, described as a Waddington concerted elimination, is reported herein. This reaction, when viable, is generally more favorable than other reactions. The results presented here are of interest to combustion modelers and atmospheric chemists, particularly those working on aromatic hydrocarbons and systems with conjugated double bonds.​