A deeper computational look at Mumm rearrangement: Evaluation of substituent, solvent, and temperature effects

The effect of substitution, solvent, and temperature on Mumm rearrangement has been investigated using density functional theory (DFT). A potential energy surface (PES) profiles of transition state (TS) is demonstrated to illustrate the alteration of ΔG‡ of Mumm rearrangements for various substitutions. The possible reasons have been studied for the impressive conditions needed for Mumm rearrangement. In summary, the results showed that the substituent effect on Mumm rearrangement depends on the nature and position. The polar solvents decrease the activation barrier whereas, nonpolar solvent increase the ΔG‡ value. In addition, the Mumm rearrangement shows a little dependency to temperature and will be done a bit faster with elevation of temperature.