Unexpected Smiles Rearrangement During Borane Reduction of 2-Aryloxy-2-methylpropionamides

Abstract

2-Nitrophenols spontaneously rearrange during alkyl­ation with 2-bromo-2-methylpropionamide in the presence of cesium carbonate in acetonitrile to the corresponding 2-hydroxy-2-methyl-N-(2-nitrophenyl)propionamides. Upon reduction of 2-aryloxy-2-methylpropionamides, which were obtained from 2-nitrophenols in three steps, with borane dimethyl sulfide complex in THF, a Smiles rearrangement was observed as well leading to 2-methyl-1-phenyl­aminopropan-2-ols. Both approaches give access to valuable 2-nitro substituted aniline derivatives.

Key words

Smiles rearrangement - reduction - amide - amine - borane/dimethyl sulfide complex

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