2-Aminophenols Containing Electron-Withdrawing Groups from N-Aryl Hydroxylamines

Abstract

Reaction of substituted N-aryl hydroxylamines with methanesulfonyl chloride, p-toluenesulfonyl chloride, or trifluoromethanesulfonic anhydride under basic conditions leads to the rearranged 2-aminophenols (45-94%). The overall reaction sequence can be performed using polymer-supported sulfonyl chloride resin allowing for the effective conversion of N-aryl hydroxylamines to the 2-aminophenols without the need for chromatography.

Key words

rearrangement - hydroxylamine - solid-phase synthesis - 2-aminophenol

References and Notes

• 1 Boyd GV. In Science of Synthesis: Methods of Molecular Transformations (Houben-Weyl)   Vol. 11:  Scheumann E. Thieme; Stuttgart: 2002.  p.481-492  
• 2 Porzelle A. Woodrow MD. Tomkinson NCO. Org. Lett.  2010,  12:  812 
• 3 Gelman D. Buchwald SL. Angew. Chem. Int. Ed.  2003,  42:  5993 
• 4 Andersen KK. Bray DD. Chumpradit S. Clark ME. Habgood GJ. Hubbard CD. Young KM. J. Org. Chem.  1991,  56:  6508 
• 5 Lévai A. Heterocycles  2008,  75:  2155 
• 6 Porzelle A. Woodrow MD. Tomkinson NCO. Eur. J. Org. Chem.  2008,  5135 
• 7 Porzelle A. Woodrow MD. Tomkinson NCO. Org. Lett.  2010,  12:  1492 
• 8a Jones KL. Porzelle A. Hall A. Woodrow MD. Tomkinson NCO. Org. Lett.  2008,  10:  797 
• 8b Porzelle A. Woodrow MD. Tomkinson NCO. Org. Lett.  2009,  11:  233 
• 9 Porzelle A. Woodrow MD. Tomkinson NCO. Synlett  2009,  798 
• 10 Gassman PG. Granrud JE. J. Am. Chem. Soc.  1984,  106:  1498 
• 11 Metal-Catalyzed Cross-Couling Reactions   2nd ed.:  de Meijere A. Diederich F. Wiley-VCH; Weinheim: 2004. 
• 12a Yang BH. Buchwald SL. J. Organomet. Chem.  1999,  576:  125 
• 12b Ritter K. Synthesis  1993,  735 

13

All rearrangement products were characterised by ^¹H NMR, ^¹³C NMR, LRMS, and HRMS.