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Synlett 2010(13): 1997-2001  
DOI: 10.1055/s-0030-1258130
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© Georg Thieme Verlag Stuttgart ˙ New York

Rasta Resin-PPh3 and its Use in Chromatography-Free Wittig Reactions

Peter Shu-Wai Leung, Yan Teng, Patrick H. Toy*
Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, P. R. of China
Fax: +85228571586; e-Mail: phtoy@hku.hk;
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Publication History

Received 19 April 2010
Publication Date:
09 July 2010 (online)

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Abstract

Rasta resin-PPh3, a new heterogeneous polystyrene-based phosphine, has been synthesized and used in one-pot Wittig olefination reactions of aldehydes. In these reactions an excess of rasta resin-PPh3 was used for the in situ generation of the phosphorane reactant and allowed for isolation of a high yield of very pure alkene product after only filtration and solvent removal. The excellent results obtained in this study are attributed to the flexible nature of the rasta resin structure, which makes it less dependant upon swelling than other heterogeneous polystyrene materials previously used to support phosphine reagents in Wittig reactions.

Key words

polymer-supported reagent - polystyrene - phosphine - phosphorane - Wittig reaction

    References and Notes

  • 1a Wittig G. Geissler G. Liebigs Ann. Chem.  1953,  580:  44 
    Google Scholar
  • 1b Wittig G. Schollkopf U. Chem. Ber.  1954,  87:  1318 
    Google Scholar
  • 2 Constable DJC. Dunn PJ. Hayler JD. Humphrey GR. Leazer JL. Linderman RJ. Lorenz K. Manley J. Pearlman BA. Wells A. Zaks A. Zhang TY. Green Chem.  2007,  9:  411 
    CrossrefGoogle Scholar
  • For the use of a phosphine catalyst in Wittig reactions, see:
  • 3a O’Brien CJ. Tellez JL. Nixon ZS. Kang LJ. Carter AL. Kunkel SR. Przeworski KC. Chass GA. Angew. Chem. Int. Ed.  2009,  48:  6836 
    Google Scholar
  • 3b Marsden SP. Nature Chem.  2009,  1:  685 
    Google Scholar
  • For the use of arsine or telluride catalysts in Wittig reactions, see:
  • 4a Shi L. Wang W. Wang Y. Huang Y.-Z. J. Org. Chem.  1989,  54:  2027 
    Google Scholar
  • 4b Huang Z.-Z. Ye S. Xia W. Yu Y.-H. Tang Y. J. Org. Chem.  2002,  67:  3096 
    Google Scholar
  • 4c Huang Z.-Z. Tang Y. J. Org. Chem.  2002,  67:  5320 
    Google Scholar
  • 4d Cao P. Li C.-Y. Kang Y.-B. Xie Z. Sun X.-L. Tang Y. J. Org. Chem.  2007,  72:  6628 
    Google Scholar
  • 5a Camps F. Castells J. Font J. Vela F. Tetrahedron Lett.  1971,  1715 
    Google Scholar
  • 5b McKinley SV. Rakshys JW.
    J. Chem. Soc., Chem. Commun.  1972,  134 
    Google Scholar
  • 5c Heitz W. Michels R. Angew. Chem., Int. Ed. Engl.  1972,  11:  298 
    Google Scholar
  • 5d Clarke SD. Harrison CR. Hodge P. Tetrahedron Lett.  1980,  21:  1375 
    Google Scholar
  • 5e Akelah A. Eur. Polym. J.  1982,  18:  559 
    Google Scholar
  • 5f Bernard M. Ford WT. Nelson EC. J. Org. Chem.  1983,  48:  3164 
    Google Scholar
  • 6 Westman J. Org. Lett.  2001,  3:  3745 
    CrossrefGoogle Scholar
  • 7a Wu J. Yue C. Synth. Commun.  2006,  36:  2939 ; and references cited therein
    Google Scholar
  • 7b Choudary BM. Mahendar K. Kantam ML. Ranganath KVS. Athar T. Adv. Symth. Catal.  2006,  348:  1977 
    Google Scholar
  • 7c El-Batta A. Jiang C. Zhao W. Anness R. Cooksy AL. Bergdahl M. J. Org. Chem.  2007,  72:  5244 
    Google Scholar
  • For cross-linked polymers, see:
  • 8a Kwok M. Choi W. He HS. Toy PH. J. Org. Chem.  2003,  68:  9831 
    Google Scholar
  • 8b Zhao LJ. He HS. Shi M. Toy PH. J. Comb. Chem.  2004,  6:  680 
    Google Scholar
  • For non-cross-linked polymers, see:
  • 9a Harned AM. He HS. Toy PH. Flynn DL. Hanson PR. J. Am. Chem. Soc.  2005,  127:  52 
    Google Scholar
  • 9b He HS. Yan JJ. Shen R. Zhuo S. Toy PH. Synlett  2006,  563 
    Google Scholar
  • 9c Kwong CK.-W. Huang R. Zhang M. Shi M. Toy PH. Chem. Eur. J.  2007,  13:  2369 
    Google Scholar
  • 10 Zhao L.-J. Kwong CK.-W. Shi M. Toy PH. Tetrahedron  2005,  61:  12026 
    CrossrefGoogle Scholar
  • 11 Bernard M. Ford WT. J. Org. Chem.  1983,  48:  326 
    CrossrefGoogle Scholar
  • 12 Lu J. Toy PH. Chem. Rev.  2009,  109:  815 
    CrossrefGoogle Scholar
  • 13a Hodges JC. Harikrishnan LS. Ault-Justus S. J. Comb. Chem.  2000,  2:  80 
    Google Scholar
  • 13b Lindsley CW. Hodges JC. Filzen GF. Watson BM. Geyer AG. J. Comb. Chem.  2000,  2:  550 
    Google Scholar
  • 13c McAlpine SR. Lindsley CW. Hodges JC. Leonard DM. Filzen GF. J. Comb. Chem.  2001,  3:  1 
    Google Scholar
  • 13d Wisnoski DD. Leister WH. Strauss KA. Zhao Z. Lindsley CW. Tetrahedron Lett.  2003,  44:  4321 
    Google Scholar
  • 13e Fournier D. Pascual S. Montembault V. Haddleton DM. Fontaine L. J. Comb. Chem.  2006,  8:  522 
    Google Scholar
  • 13f Fournier D. Pascual S. Montembault V. Fontaine L. J. Polym. Sci. A: Polym. Chem.  2006,  44:  5316 
    Google Scholar
  • 13g Pawluczyk JM. McClain RT. Denicola C. Mulhearn JJ. Rudd DJ. Lindsley CW. Tetrahedron Lett.  2007,  48:  1497 
    Google Scholar
  • 13h Chen G. Tao L. Mantovani G. Geng J. Nystroem D. Haddleton DM. Macromolecules  2007,  40:  7513 
    Google Scholar
  • 14a Toy PH. Janda KD. Tetrahedron Lett.  1999,  40:  6329 
    Google Scholar
  • 14b Toy PH. Reger TS. Janda KD. Aldrichimica Acta  2000,  33:  87 
    Google Scholar
  • 14c Toy PH. Reger TS. Garibay P. Garno JC. Malikayil JA. Liu G.-Y. Janda KD.
    J. Comb. Chem.  2001,  3:  117 
    Google Scholar
  • 14d Choi MKW. Toy PH. Tetrahedron  2004,  60:  2903 
    Google Scholar
  • 17a Yano T. Kuroboshi M. Tanaka H. Tetrahedron Lett.  2010,  51:  698 
    Google Scholar
  • 17b Yano T. Hoshimo M. Kuroboshi M. Tanaka H. Synlett  2010,  801 
    Google Scholar
15

See Supporting Information for details.

16

General Procedure for Wittig Reactions To a solution of the aldehyde (0.5 mmol) and the alkyl halide (0.75 mmol) in the appropriate solvent (5 mL), was added RR-PPh3 (1.0 mmol), followed by Et3N (1.0 mmol). The reaction mixture was stirred at the indicated temperature until TLC analysis indicated that the aldehyde was completely consumed, and then filtered through a plug of silica gel. After washing the polymer with CH2Cl2 (2 × 50 mL) the combined filtrate was concentrated in vacuo to afford pure product. All alkene products were characterized by ¹H NMR and ¹³C NMR spectroscopy. Steroeoisomeric ratios were determined by ¹H NMR spectroscopy.