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Bromo-nitro substitution on a tertiary α carbon - A previously uncharacterized facet of the Kornblum substitution

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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<inf>N</inf>1/S<inf>N</inf>2 mechanism domain for Kornblum substitutions. 2015

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