tert‐Butyl Nitrite Mediated Nitro‐Nitratosation of Internal Alkenes

In an oxygen atmosphere tert ‐butyl nitrite (TBN) reacts with unsymmetrical internal benzylic alkenes giving nitro‐nitratosation product exclusively. The γ ‐diaryl‐substituted styrenes provided better yields compared to γ ‐alkyl‐aryl‐substituted styrenes. The higher yields for the former type of substrates is possibly dictated by the additional stability of benzylic radical due to the anchimeric assistance imparted by the γ ‐substituted phenyl ring. During oxidative nitration, the nitro (NO 2 ) group adds at the non‐benzylic site, whereas the nitrato group (ONO 2 ) is attached at the relatively stable benzylic position. Under similar reaction conditions, α,β ‐unsaturated carboxylic acids, afforded nitroalkenes as the sole product.