O-Allylic Substitution of Hydroxylamine Derivatives Having an N-Electron-Withdrawing Substituent

Abstract

The O-allylic substitution of hydroxylamines having an N-electron-withdrawing substituent proceeded smoothly to afford O-allylated products by using [IrCl(cod)]₂ or Pd(PPh₃)₄.

Key words

allylations - iridium - palladium - cyclizations - meta­thesis

References

• For recent reviews, see:
• 1a Johannsen M. Jorgensen KA. Chem. Rev.  1998,  98:  1689 
• 1b Trost BM. Chem. Pharm. Bull.  2002,  50:  1 
• 2a Keinan E. Sahai M. Roth Z. J. Org. Chem.  1985,  50:  3558 
• 2b Trost BM. Tenaglia A. Tetrahedron Lett.  1988,  29:  2931 
• 2c Goux C. Massacret M. Lhoste P. Sinou D. Organometallics  1995,  14:  4585 
• 2d Satoh T. Ikeda M. Miura M. Nomura M. J. Org. Chem.  1997,  62:  4877 
• 2e Trost BM. McEachern EJ. Toste FD. J. Am. Chem. Soc.  1998,  120:  12702 
• 2f Konno T. Nagata K. Ishihara T. Yamanaka H. J. Org. Chem.  2002,  67:  1768 
• 3a Evans PA. Leahy DK. J. Am. Chem. Soc.  2002,  124:  7882 
• 3b Kim H. Lee C. Org. Lett.  2002,  4:  4369 
• Procedures for preparing the allylated hydroxylamines often require lengthy linear manipulation. See:
• 4a Bull SD. Davies SG. Domingez SH. Jones S. Price AJ. Sellers TGR. Smith AD. J. Chem. Soc., Perkin Trans. 1  2002,  2141 
• 4b Ishikawa T. Kawakami M. Fukui M. Yamashita A. Urano J. Saito S. J. Am. Chem. Soc.  2001,  123:  7734 
• 5a Murahashi S. Imada Y. Taniguchi Y. Kodera Y. Tetrahedron Lett.  1988,  29:  2973 
• 5b Genet J.-P. Thorimbert S. Touzin A.-M. Tetrahedron Lett.  1993,  34:  1159 
• The iridium-catalyzed regioselective allylic amination was recently achieved by Takeuchi’s group. See:
• 6a Takeuchi R. Ue N. Tanabe K. Yamashita K. Shiga N. J. Am. Chem. Soc.  2001,  123:  9525 
• 6b Takeuchi R. Shiga N. Org. Lett.  1999,  1:  265 
• 6c For a review, see: Takeuchi R. Synlett  2002,  1954 
• 7 Recently, the effect of a hydroxylamine tether on intramolecular Diels-Alder reactions was reported. See: Ishikawa T. Senzaki M. Kadoya R. Morimoto T. Miyake N. Izawa M. Saito S. J. Am. Chem. Soc.  2001,  123:  14607 
• For recent reviews on ring-closing methathesis, see:
• 8a Grubbs RH. Tetrahedron  1998,  54:  4413 
• 8b Pandit UK. Overleeft HS. Borer BC. Bieraugel H. Eur. J. Org. Chem.  1999,  9 

9

The cyclic products 14c-e were obtained as a diastereomeric mixture in about 10:1 ratio by ¹H NMR, although these stereochemistries have not be determined.