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Synthesis 2004(6): 923-927
DOI: 10.1055/s-2004-815996
DOI: 10.1055/s-2004-815996
PAPER
© Georg Thieme Verlag Stuttgart · New YorkP-BEMP: A New Efficient and Commercially Available User-Friendly and Recyclable Heterogeneous Organocatalyst for the Michael Addition of 1,3-Dicarbonyl Compounds
Further Information
Received
23 October 2003
Publication Date:
04 March 2004 (online)
Publication History
Publication Date:
04 March 2004 (online)
Abstract
Michael addition of 1,3-dicarbonyls with various Michael acceptors has been found to be catalyzed by commercially available, user-friendly and recyclable N-phenyl-tris(di-methylamino)iminophosphorane immobilized on polystyrene resin (P-BEMP). The reaction does not require anhydrous solvents or inert atmosphere and proceeds smoothly at room temperature leading to the corresponding adducts, which can be conveniently isolated in high yield and with high chemical purity by simple filtration.
Key words
1,3-dicarbonyls - heterogeneous catalysis - Michael addition - polymer supported iminophosphoranes
- 1a
Bergman ED.Ginsburg D.Pappo R. Org. React. 1959, 10: 179 - 1b
House HO. Modern Synthetic Reactions 2nd ed.: W. A. Benjamin Inc.; Menlo Park: 1972. p.595 - 1c
Jung ME. In Comprehensive Organic Synthesis Vol. 4:Trost BM.Fleming I.Semmelhack MF. Pergamon; Oxford: 1991. p.1 - 1d
Perlmutter P. Conjugate Addition Reactions in Organic Synthesis Pergamon; Oxford: 1992. - 2a For a recent account, see:
Rodriguez J. Synlett 1999, 505 - 2b For some recent examples from this laboratory, see:
Simon C.Peyronel JF.Rodriguez J. Org. Lett. 2001, 3: 2145 - 2c See also:
Guillaume M.Dumez E.Rodriguez J.Dulcère JP. Synlett 2002, 1883 - 2d See also:
Simon C.Peyronel JF.Clerc F.Rodriguez J. Eur. J. Org. Chem. 2002, 3359 - See inter alia:
- 3a
Ouvrard N.Rodriguez J.Santelli M. Angew. Chem., Int. Ed. Engl. 1992, 31: 1651 - 3b See also:
Shibasaki M.Sasai H.Arai T. Angew. Chem. Int. Ed. 1997, 36: 1236 - 3c For recent reviews on enantioselective Michael additions, see:
Krause N.Hoffmann-Röder A. Synthesis 2001, 171 - 3d See also:
Christoffers J.Mann A. Chem. Eur. J. 2001, 7: 1014 - 3e See also:
Berner OM.Tedeschi L.Enders D. Eur. J. Org. Chem. 2002, 1877 - See inter alia:
- 4a
Alexakis A.Chapdelaine MJ.Posner GH. Tetrahedron Lett. 1978, 4209 - 4b
Filippini M.-H.Faure R.Rodriguez J. J. Org. Chem. 1995, 60: 6872 - 4c
Ballini R.Barboni L.Bosica G.Filippone P.Peretti S. Tetrahedron 2000, 56: 4095 - For recent reviews, see:
- 5a
Christoffers J. Eur. J. Org. Chem. 1998, 1259 - 5b See also:
Christoffers J. Synlett 2001, 723 - 5c See also:
Keller E.Feringa BL. Tetrahedron Lett. 1996, 37: 1879 - 5d See also:
Keller E.Feringa BL. Synlett 1997, 842 - 5e See also:
Mori Y.Kakumoto K.Manabe K.Kobayashi S. Tetrahedron Lett. 2000, 41: 3107 - For recent contributions, see:
- 6a
Bensa D.Brunel J.-M.Buono G.Rodriguez J. Synlett 2001, 715 - 6b See also:
Muthusamy S.Babu AS.Gunanathan C. Synth. Commun. 2002, 32: 3247 - 6c See also:
Grossman RB.Comesse S.Rasne RM.Hattori K.Delong MN. J. Org. Chem. 2003, 68: 871 - 6d See also:
Wroblewski AE.Bansal V.Kisanga P.Verkade JG. Tetrahedron 2003, 59: 561 - For recent reviews and accounts, see:
- 7a
Dalko PI.Moisan L. Angew. Chem. Int. Ed. 2001, 40: 3726 - 7b See also:
Gröger H.Wilken J. Angew. Chem. Int. Ed. 2001, 40: 529 - 7c
Jarvo ER.Miller SJ. Tetrahedron 2002, 58: 2481 - 7d
List B. Synlett 2001, 1675 - 7e
List B. Tetrahedron 2002, 58: 5573 - 8a
Metzger JO. Angew. Chem. Int. Ed. 1998, 37: 2975 - 8b
Kotsuki H.Arimura K.Ohishi T.Maruzasa R. J. Org. Chem. 1999, 64: 3770 - 8c
Tanaka K.Toda F. Chem. Rev. 2000, 100: 1025 - 9a
Posner GH. Synthesis 1978, 487 - 9b
Laszlo P. Acc. Chem. Res. 1986, 19: 121 - 9c
Kloetstra R.Bekkum HV. J. Chem. Soc., Chem. Commun. 1995, 1005 - 9d
Kabalka GW.Pagni RM. Tetrahedron 1997, 53: 7999 - 10a
Hodge P.Khoshdel E.Waterhouse J. J. Chem. Soc., Chem. Commun. 1983, 2205 - 10b
Bandgar BP.Zirange MB.Wadgaonkar PP. Synlett 1996, 149 - 10c
Macquairrie DJ. Tetrahedron Lett. 1998, 39: 4125 - 10d
Fava C.Galeazzi R.Gonzalez-Rosende EM.Orena M.Macquairrie DJ. Tetrahedron Lett. 1998, 39: 4125 - 11a
McKillop A.Young DW. Synthesis 1979, 401 - 11b
McKillop A.Young DW. Synthesis 1979, 481 - 11c
Laszlo P.Pennetreau P. Tetrahedron Lett. 1985, 26: 2645 - 11d
Laszlo P.Montaufier M.-T.Randriamahefa SL. Tetrahedron Lett. 1990, 31: 4867 - 11e
Kotsuki H.Arimura K. Tetrahedron Lett. 1997, 38: 7583 - 11f
Mdoe JEG.Clark JH.Macquarrie DJ. Synlett 1998, 625 - 11g
Choudary BM.Kantan ML.Kativa B.Reddy ChV.Figueras F. Tetrahedron 2000, 56: 9357 - 11h
Tateiwa J.-I.Hosomi A. Eur. J. Org. Chem. 2001, 1445 - 12a
Hattori H. Chem. Rev. 1995, 95: 537 - 12b
Mizuno N.Misono M. Chem. Rev. 1998, 98: 199 - 12c See also a special issue on heterogeneous catalysis: Chem. Rev. 1995, 95: 475
- 12d For a recent exemple, see:
Ballini R.Bosica G.Livi D.Palmieri A.Maggi R.Sartori G. Tetrahedron Lett. 2003, 44: 2271 - For recent reviews, see:
- 13a
Shuttleworth S.Allin SM.Sharma PK. Synthesis 1997, 1217 - 13b
Clapham B.Reger TS.Janda KD. Tetrahedron 2001, 57: 4637 - 14 For a special issue on environmental chemistry, see: Chem. Rev. 1995, 95: 1
- 15 For a recent example, see:
Shibatomi K.Nakahashi T.Uozumi Y. Synlett 2000, 1643 - 16
Hagiwara H.Sayuri T.Okabe T.Hoshi T.Suzuki T.Suzuki H.Shimizu K.-i.Kitayama Y. Green Chem. 2002, 4: 461 - 17a
Legrand O. Synlett 1999, 752 - 17b See also a special issue on strong and hindered bases: Chem. Files, Fluka 2003, 3: No. 1
- For Michael additions promoted by the so-called P1, P2 and P4 phosphazene bases, see:
- 18a
Pietzonka T.Seebach D. Angew. Chem., Int. Ed. Engl. 1993, 32: 716 - 18b See also:
Solladié-Cavallo A.Koessler JL.Isarno T.Roche D.Andriamiadanarivo R. Synlett 1997, 217 - 18c See also:
Paulitz C.Steglich W. J. Org. Chem. 1997, 62: 8474 - 18d See also:
Solladié-Cavallo A.Diep-Vohuule A.Isarno T. Angew. Chem., Int. Ed. 1998, 37: 1689 - 18e
Costa A.Najera C.Sansano JM. J. Org. Chem. 2002, 67: 5216 - Recently nonsupported P1 BEMP and related BTPP iminophosphoranes used in large excess have been shown to promote some specific Michael additions with ethyl acetoacetate, nitroarenes and Schiff base esters:
- 19a
Richter H.Walk T.Höltzel A.Jung G. J. Org. Chem. 1999, 64: 1362 - 19b See also:
Lash T.Thompson ML.Werner TM.Spence JD. Synlett 2000, 213 - 19c
O’Donnell MJ.Delgado F.Domínguez E.de Blas J.Scott WL. Tetrahedron: Asymmetry 2001, 12: 821 - 19d For utilization of a related synthetic P1 polymer supported iminophosphorane base
in the acylation of alcohols, see:
Ilankumaran P.Verkade JG. J. Org. Chem. 1999, 64: 9063 - 20 For an example of synthetic utilization of the corresponding Michael adduct, see:
Chareyron M.Devin P.Fensterbank L.Malacria M. Synlett 2000, 83 - 21 For the first example of a supported proline-derived organocatalyst used in the kinetic
resolution of racemic alcohols, see:
Pelotier B.Priem G.Campbell IB.Macdonald SJF.Anson MS. Synlett 2003, 679 - 22
Yamaguchi M.Yokota N.Minami T. J. Chem. Soc., Chem. Commun. 1991, 1088 - 24
Brunel J.-M.Legrand O.Reymond S.Buono G. J. Am. Chem. Soc. 1999, 121: 5807 - 25
Molander GA.Kenny C. J. Am. Chem. Soc. 1989, 111: 8236 - 26
Grigg R.Thornton-Pett M.Yoganathan G. Tetrahedron 1999, 55: 1763 - 27
Christoffers J. J. Chem. Soc., Perkin Trans. 1 1997, 3141 - 28
Christoffers J.Rößler U.Werner T. Eur. J. Org. Chem. 2000, 701 - 29
Gomez-Bengoa E.Cuerva JM.Mateo C.Echavarren AM. J. Am. Chem. Soc. 1996, 118: 8553 - 30
Still WC.Kahn M.Mitra A. J. Org. Chem. 1978, 43: 2923
References
After the first reaction the color of the catalyst changed from yellow to brown, but this modification remains insensitive towards the catalytic activity.