Mechanistic Insights for Nitromethane Activation into Reactive Nitrogenating Reagents

Recently, it was found that nitromethane (CH3NO2) can be activated into a useful nitrogenating reagent for the synthesis of amide and nitrile compounds. In this work, mechanisms CH3NO2 activation are explored in detail by extensive DFT calculations. aqueous triflic acid (HOTf) solution, formal 1,3-H-shift transient CH2=NO2H is identified as rate-limiting step over barrier 29.6 kcal/mol, followed multistep hydrolysis to cleave C=N bond form NH3OH+ (and HCOOH) final product. contrast, non-aqueous acetic (AcOH) solution with electrophilic Tf2O nucleophilic HCOOH additives, cleaved sequential steps H2O elimination, activation, addition acetate/TfO? exchange, affording AcONH3+ more reactive Beckmann-type reactions.