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Synthesis 2005(4): 639-643
DOI: 10.1055/s-2004-837302
DOI: 10.1055/s-2004-837302
PAPER
© Georg Thieme Verlag Stuttgart · New York
Unexpected Smiles Rearrangement During Borane Reduction of 2-Aryloxy-2-methylpropionamides
Further Information
Received
22 October 2004
Publication Date:
22 December 2004 (online)
Publication History
Publication Date:
22 December 2004 (online)
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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