(-)O R1 R1
R1-CH-R2 tBuOK | | H2O DMD aq NH4Cl |
| -----------------> (+)N=CH -------> -------> --------> C=O
NO2 THF/ca 20°C/5 min | | 2 min 5 min |
(-)O R2 R2
(1) (2) (3)
TABLE 1
ENTRY SUBSTRATE H2O(eqv) DMD(eqv) PRODUCT YIELD(%) (*)
1 Et-C(-NO2)-C2H4-COOMe 0 1.2 Et-C(=O)-C2H4-COOMe 67
2 1.0 1.2 90
3 (**) 1.0 1.2 64
4 Et-C(-NO2)-C2H4-C(=O)-Me 0 1.2 Et-C(=O)-C2H4-C(=O)-Me 56
5 (**) 1.0 1.2 80
6 1.0 1.2 99
7 Et-C(-NO2)-C2H4-CN 1.0 1.2 Et-C(=O)-C2H4-CN 86
8 O2N-CH-(C2H4-COOMe)2 1.0 1.2 O=CH-(C2H4-COOMe)2 83
9 O2N-C3H6-COOMe 1.0 1.2 OHC-C2H4-COOMe 73
(*) Yield of isolated product after silica gel chromatography; products 3a [17],
3b [18], 3c [19], 3d [20] and 3e [21] have identical spectral data and physical
constants as those reported.
(**) Water was added after DMD
1a = Et-C(-NO2)-C2H4-COOMe
1b = Et-C(-NO2)-C2H4-C(=O)-Me
1c = Et-C(-NO2)-C2H4-CN
1d = O2N-CH-(C2H4-COOMe)2
1e = O2N-C3H6-COOMe
3a = Et-C(=O)-C2H4-COOMe
3b = Et-C(=O)-C2H4-C(=O)-Me
3c = Et-C(=O)-C2H4-CN
3d = O=CH-(C2H4-COOMe)2
3e = OHC-C2H4-COOMe
Acknowledgement: Generous financial support of the Deutsche Forschungsgemeinschaft (Schwerpunktprogramm: Peroxidchemie) and the Fonds der Chemischen Industrie is gratefully appreciated. M. Makosza thanks the Alexander von Humboldt Foundation for the research award which made this collaboration possible. C.-G. Z. thanks the DAAD (Deutscher Akademischer Austauschdienst) for a doctoral fellowship.
References and Notes:
(1) Seebach, D.; Colvin, E. W.; Lehr, F.; Weller, T. Chimia 1979, 33,1.
(2) Noland, W. E. Chem. Rev. 1955, 55, 137; Pinnick, H. W. Org. React. 1990, 38, 655.
(3) Schechter, H.; Williams, F. T. J. Org. Chem. 1962, 27, 369.
(4) Pagano, A.H.; Schechter, H. J. Org. Chem. 1970, 35, 295.
(5) McMurry, J. E.; Melton, J.; Padgett, H. J. Org. Chem. 1974, 39,259.
(6) Williams, J. R.; Unger, L. R.; Moore, R. H. J. Org. Chem. 1978,43, 1271.
(7) Ceccherelli, P.; Curini, M.; Epifano, F.; Marcotullio, M. C.;Rosati, O. Synth. Commun. 1998, 28, 3057.
(8) Bartlett, P. A.; Green III, F. R.; Webb, T. R. Tetrahedron Lett. 1977, 331.
(9) Murray, R. W.; Jeyaraman, R. J. Org. Chem. 1985, 50, 2847.
(10) Adam, W.; Bialas, J.; Hadjiarapoglou, L. P. Chem. Ber. 1991, 124, 2377.
(11) For reviews see: Adam, W.; Curci, R.; Edwards, J. O. Acc. Chem. Res. 1989, 22, 205; Murray, R. W. Chem. Rev. 1989, 89, 1187; Curci, R. In Advances in Oxygenated Process; Baumstark, A. L. Ed.; JAI: Greenwich CT, 1990, Vol 2, Chapter I, pp 1; Adam, W.; Hadjiarapoglou, L. P.; Curci, R.; Mello, R. In Organic Peroxides; Ando, W. Ed.; Wiley: New York, 1992, Chapter 4, pp 195; Curci, R.; Dinoi, A.; Rubino, M. F. Pure Appl. Chem. 1995, 67, 811; Adam, W.; Smerz, A. K. Bull. Soc. Chim. Belg. 1996, 105, 581; Adam, W.; Smerz, A. K.; Zhao, C.-G. J. Prakt. Chem. 1997, 339, 298.
(12) Curci, R.; D’Accolti, L.; Fiorentino, M.; Fusco, C.; Adam, W. González-Nuñez, M. E.; Mello, R. Tetrahedron Lett. 1992, 33, 4225.
(13) Altamura, A.; Curci, R.; Edwards, J. O. J. Org. Chem. 1993, 58, 7289.
(14) Adam, W.; Ma, kosza, M.; Stalin`ski, K.; Zhao, C.-G. J. Org. Chem 1998, 63, 4390.
(15) Ballini, R.; Bosica, G. Eur. J. Org. Chem. 1998, 355; Ballini, R.; Bosica, G. Tetrahedron Lett. 1996, 44, 8027.
(16) Chasar, D. W. Synthesis 1982, 841-842.
(17) Baldwin, J. E.; Adlington, R. M.; Jain, A. U.; Kolhe, J. N.; Perry, M. W. D. Tetrahedron 1986, 42, 4247.
(18) Macias, F. A.; Molinillo, J. M. G.; Massanet, G. M.; Rodriguez-Luis, F. Tetrahedron 1992, 48, 3345.
(19) Coveney, D. J.; Patel, V. F.; Pattenden, G.; Thompson, D. M. J. Chem. Soc., Perkin Trans. 1 1990, 2721.
(20) Huisgen, R.; Fliege, W.; Kolbeck, W. Chem. Ber. 1983, 116, 3027.
(21) Ono, N.; Katayama, H.; Nisyiyama, S.; Ogawa, T. J. Heterocycl. Chem. 1994, 31, 707.
(22) Baumstark, A. L.; Vasquez, P. C. J. Org. Chem. 1988, 53, 3437; Murray, R. W.; Gu, D. J. Chem. Soc., Perkin Trans. 2, 1993, 2203; Murray, R. W.; Gu, D. Ibid. 1994, 451; Buxton, P. C.; Ennis, J. N.; Marples, B.A.; Waddington, V. L.; Boehlow, T. R. Ibid. 1998, 265.
(23) Miaskiewicz, K.; Teich, N. A.; Smith, D. A. J. Org. Chem. 1997, 62, 6493.
(24) General Procedure: To a solution of the nitroalkane (1.0 mmol) in THF (10 mL, freshly distilled over potassium) was added t-BuOK (123 mg, 1.1 mmol) and the mixture was stirred at room temperature (ca. 20 °C) for 5 min. Then H2O (18.0 mL, 1.0 mmol) was added, stirred for 2 min, and a solution of DMD (1.2 mmol, 0.07-0.10 M) in acetone (dried over molecular sieves 4Å) was added in one portion. After 5 min, the reaction mixture was neutralized with aqueous NH4Cl (0.5 mL) and dried over MgSO4. The MgSO4 was removed by filtration and washed with acetone (3´10 mL). The crude product, obtained after evaporation (20 °C, 30 mbar) of the solvent, was purified by silica gel chromatography with 30-50% ether in petroleum ether (b.p. 30-50 °C) as eluent (1:1 EtOAc/n-hexane was used for 3d).