Synthesis 2005(4): 639-643  
DOI: 10.1055/s-2004-837302
PAPER
© Georg Thieme Verlag Stuttgart · New York

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

Hans-Peter Buchstaller*, Uwe Anlauf
Merck KGaA, Medicinal Chemistry Research Laboratories, Frankfurter Str. 250, 64271 Darmstadt, Germany
Fax: +49(6151)723129; e-Mail: hans.peter.buchstaller@merck.de;
Further Information

Publication History

Received 22 October 2004
Publication Date:
22 December 2004 (eFirst)

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.

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