LETTER
Highly Efficient Phosphazene Base-Catalyzed Michael Addition
717
Blacky Academic and Professional: London, 1998. Lubineau,
(14) Brunel, J.-M.; Legrand, O.; Reymond, S.; Buono, G. J. Am.
Chem. Soc. 1999, 121, 5807. Legrand, O. Synlett 1999, 752.
(15) We have checked the stability of N-phenyl-tris(dimethyl-
amino)iminophosphorane in water over a period of 96 hours
A.; Augé, J. In Modern Solvents in Organic Synthesis, Topics
in Current Chemistry, Knochel, P., Ed.; Springer-Verlag:
Berlin Heidelberg, Vol. 206, p. 1-39, 1999. Venkatraman, S.;
Li, C.-J. Tetrahedron Lett. 2001, 42, 781.
3
1
by P NMR and found no significant modification of the
structure. For recent determinations of basicity scales
including N-phenyl-tris(dimethylamino)iminophosphorane,
see: Rodima, T.; Mäemets, V.; Koppel, I. A. J. Chem. Soc.,
Perkin Trans. 1 2000, 2637. Kaljurand, I.; Rodima, T.; Leito,
I.; Koppel, I. A.; Schwesinger, R. J. Org. Chem. 2000, 65,
6202.
(
(
2) Anastas, P. T.; Williamson, T. C. In Green Chemistry:
Frontiers in Benign Chemical Syntheses and Processes,
Oxford University Press, 1998.
3) Trost, B. M. Science 1991, 254, 1471. Sheldon, R., Chem. Ind.
(London) 1992, 903. Trost, B. M. Angew. Chem., Int. Ed.
Engl. 1995, 34, 259. Trost, B. M.; Krische, M. J. Synlett 1998,
1
.
(16) For preparation of trans-2-arylcyclopropane carboxylates by
condensation of a Michael acceptor to an ylide mediated by
P2Et and a chiral sulfonium salt, see: Solladié-Cavallo, A.;
Diep-Vohuule, A.; Isarno, T. Angew. Chem., Int. Ed. Engl.
1998, 37, 1689.
(
(
4) (a) Keller, E.; Feringa, B. L. Tetrahedron Lett. 1996, 37, 1879.
b) Keller, E.; Feringa, B. L. Synlett 1997, 842.
(
5) Mori, Y.; Kakumoto, K.; Manabe, K.; Kobayashi, S.
Tetrahedron Lett. 2000, 41, 3107.
(
(
6) Shibatomi, K.; Nakahashi, T.; Uozumi, Y. Synlett 2000, 1643.
7) For a recent account, see: Rodriguez, J. Synlett 1999, 505. See
also: Durand, A. C.; Dumez, E.; Rodriguez, J.; Dulcère, J.-P.
Chem. Commun. 1999, 2427. Durand, A. C.; Dumez, E.;
Rodriguez, J.; Dulcère, J.-P. Synlett 2000, 731.
(17) Vetter, H.-J.; Nöth, H. Chem. Ber. 1963, 96, 1308. Goldwhite,
H.; Gysegem, P.; Schow, S.; Swyke, C. J. Chem. Soc., Dalton
Trans. 1975, 16. Bellan, J.; Marre, M. R.; Sanchez, M.; Wolf,
R. Phosphorus and Sulfur 1981, 12, 11. Shevchenko, M. V.;
Kukhar, V. P. J. Gen. Chem. USSR (Engl. Transl.) 1986, 73.
Shevchenko, M. V.; Kukhar, V. P. Zh. Obshch. Khim. 1986,
56, 85. Jiansheng, T.; Dopke, J.; Verkade, J. G. J. Am. Chem.
Soc. 1993, 115, 5015.
(
8) Eder, U.; Sauer, G.; Wiechert, R. Angew. Chem., Int. Ed.
Engl. 1971, 10, 496. Hajos, Z. G.; Parrish, D. R. J. Org. Chem.
1974, 32, 1612. Lavallée, J.-F.; Deslongchamps, P.
Tetrahedron Lett. 1988, 29, 6033. Harada, N.; Sugioka, T.;
Uda, H.; Kuriki, T. Synthesis 1990, 53. Schick, H.; Roatsch,
B.; Schwarz, H.; Hauser, A.; Schwarz, S. Liebigs Ann. Chem.
(18) General experimental procedure: To a solution of ketoester
1 (0.5 mmol) and the corresponding acceptor 2 (1.5 mmol) in
H O (2 mL) was added N-phenyl-tris(dimethylamino)-
2
1
992, 419.
iminophosphorane (0.05 mmol). The resulting reaction
mixture was stirred at room temperature for the indicated time
(Table 1). After completion, water (10 mL) was then added to
(
9) Lubineau, A.; Augé, J. Tetrahedron Lett. 1992, 33, 8073.
Ballini, R.; Bosica, G. Tetrahedron Lett. 1996, 37, 8027.
Ballini, R.; Barboni, L.; Bosica, G.; Filippone, P.; Peretti, S.
Tetrahedron 2000, 56, 4095.
the mixture. Extraction with Et O (3 20 mL), drying
2
(Na SO ), filtration through a short pad of silica gel and
2
4
(
(
(
10) For utilization of phosphorus and aza nucleophiles in water-
promoted hetero-Michael reaction, see: Larpent, C.; Patin, H.
Tetrahedron 1988, 44, 6107. Larpent, C.; Meignan, G.; Patin,
H. Tetrahedron 1990, 46, 6381. Jenner, G. Tetrahedron 1996,
evaporation of the solvent gave compounds 3 with a very high
chemical purity (>95%) estimated by NMR. Compounds
2
0
3a,b,f have been purified by flash chromatography on silica
gel.
52, 13557.
(19) The reaction of 1a with 2c catalyzed by N-phenyl-tris(di-
methylamino) iminophosphorane in more usual organic
solvents such as THF, EtOAc, CH Cl , and acetone has been
11) See inter alia: Alexakis, A.; Chapdelaine, M. J.; Posner G. H.
Tetrahedron Lett. 1978, 4209. Filippini, M.-H.; Faure, R.;
Rodriguez, J. J. Org. Chem. 1995, 60, 6872. Ballini, R.;
Barboni, L.; Bosica, G.; Filippone, P.; Peretti, S. Tetrahedron
2
2
found totally ineffective even after prolonged reaction time or
at reflux. For other experimental conditions using organic
solvent with 3-substituted aldehydes, see: Yamaguchi, M.;
Yamaguchi, M.; Yokota, N.; Minami, T. J. Chem. Soc., Chem.
Commun. 1991, 1088. Ouvrard, N.; Rodriguez, J.; Santelli, M.
Angew. Chem., Int. Ed. Engl. 1992, 31, 1651.
2
000, 56, 4095.
12) Bergman, E. D.; Ginsburg, D.; Pappo, R. Org. React. 1959,
0, 179. House, H. O. In Modern Synthetic Reactions, 2nd ed.,
W. A. Benjamin Inc.: Menlo Park, Philippines, 1972; pp. 595-
23. Jung, M. E. In Comprehensive Organic Synthesis; Trost,
B. M.; Fleming, I., Eds.; Pergamon: Oxford, 1991; Vol. 4, pp.
-67. Perlmutter, P. Conjugate Addition Reactions in Organic
1
6
(20) Still, W. C.; Kahn, M.; Mitra, A. J. Org. Chem. 1978, 43,
2923.
1
Synthesis; Pergamon Press: Oxford, 1992.
(13) For example, reaction of 2-methylcyclopentane-1,3-dione
Article Identifier:
with acrolein using KOH/H O has been reported to give only
1437-2096,E;2001,0,05,0715,0717,ftx,en;G02801ST.pdf
2
polymeric material while in water without addition of a base
the corresponding Michael adduct was formed in 90% yield,
see: Crispin, D. J.; Vanstone, A. E.; Whitehurst, J. S. J. Chem.
Soc. C 1970, 10. For similar effect with K CO , see: Bassetti,
2
3
M.; Cerchelli, G.; Floris, B. Gazz. Chim. Ital. 1991, 121, 527.
Synlett 2001, No. 5, 715–717 ISSN 0936-5214 © Thieme Stuttgart · New York