Synlett, Table of Contents LETTER © Georg Thieme Verlag Stuttgart · New York O-Allylic Substitution of Hydroxylamine Derivatives Having an N-Electron-Withdrawing Substituent Hideto Miyabea, Kazumasa Yoshidaa, Akira Matsumuraa, Masashige Yamauchib, Yoshiji Takemoto*a a Graduate School of Pharmaceutical Sciences, Kyoto University, Yoshida, Sakyo-ku, Kyoto 606-8501, JapanFax: +81(75)7534569; e-Mail: takemoto@pharm.kyoto-u.ac.jp; b Faculty of Pharmaceutical Sciences, Josai University, Keyakidai, Sakado, Saitama 350-0295, Japan Recommend Article Abstract Buy Article All articles of this category 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 Full Text References 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.
