Controllable Activation Of Beta-Alkyl Nitroalkenes: Regioselective Synthesis Of Allyl And Vinyl Sulfones

The regiospecific radical reactions of beta-alkyl nitroalkenes with sulfonyl hydrazides depended to a great extent on the choice of a solvent and catalyst. In the presence of dimethylformamide (DMF), beta-alkyl nitroalkenes more likely converted into electron-rich allyl nitro compounds, which reacted with sulfonyl hydrazides to afford allyl sulfones with high regioselectivity. While in acetonitrile (CH3CN), vinyl sulfones were obtained directly via sulfonation of electron-deficient beta-alkyl nitroalkenes. The mechanism investigation revealed that the regioselectivity was controlled by the equilibrium of beta-alkyl nitroalkenes and allyl nitro compounds.