Bromo-nitro substitution on a tertiary α carbon-a previously uncharacterized facet of the Kornblum substitutionElectronic supplementary information (ESI) available. See DOI: 10.1039/c5ra14798k

Sodium nitrite in dimethylformamide substitutes nitro for bromine alpha to an amide carbonyl in high yield at a tertiary site. Hammett plots show a strongly positive ρ value (+0.67), indicating a negatively-charged transition state, in contrast to the typical S N 1/S N 2 mechanism domain for Kornblum substitutions. Sodium nitrite in dimethylformamide substitutes nitro for bromine alpha to an amide carbonyl in high yield at a tertiary site.