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Nitromethane as a nitrogen donor in Schmidt-type formation of amides and nitriles

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Science  17 Jan 2020:
Vol. 367, Issue 6475, pp. 281-285
DOI: 10.1126/science.aay9501

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Sourcing nitrogen from nitromethane

Nitromethane is produced in bulk quantities for use as a solvent. Its applications as a reagent have focused mainly on the acidity of the methyl protons en route to modifying the carbon center. Liu et al. now report an alternative protocol that activates the nitrogen center to produce an aminating agent. An in situ reductive reaction with triflic anhydride, formic acid, and acetic acid yields an acetylated hydroxylamine, characterized by mass spectrometry. This nitrogen donor conveniently transforms a variety of ketones and aldehydes into amides.

Science, this issue p. 281

Abstract

The Schmidt reaction has been an efficient and widely used synthetic approach to amides and nitriles since its discovery in 1923. However, its application often entails the use of volatile, potentially explosive, and highly toxic azide reagents. Here, we report a sequence whereby triflic anhydride and formic and acetic acids activate the bulk chemical nitromethane to serve as a nitrogen donor in place of azides in Schmidt-like reactions. This protocol further expands the substrate scope to alkynes and simple alkyl benzenes for the preparation of amides and nitriles.

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