4348
F. Palacios et al. / Tetrahedron Letters 45 (2004) 4345–4348
2253–2329; (b) Enders, D.; Wortymann, L. K.; Peters, R.
Acc. Chem. Res. 2000, 33, 157–169.
Acknowledgements
12. (a) Malachowski, W. P.; Tie, C.; Wang, K.; Broadrup, R.
L. J. Org. Chem. 2002, 67, 8962–8969; (b) Lee, H.; Song, J.
W.; Choi, Y. S.; Park, H. M.; Lee, K. B. J. Am. Chem.
Soc. 2002, 124, 11881–11893.
13. For reviews, see: (a) Aminophosphonic and Aminophosphi-
nic Acids. Chemistry and Biological Activity; Kukhar, V.
P., Hudson, H. R., Eds.; Wiley: Chichester, 2000; (b)
Fields, S. F. Tetrahedron 1999, 55, 12237–12273.
The authors thank the Ministerio de Ciencia y Tecno-
ꢀ
logıa (MCYT, Madrid DGI, BQU2000-0217) and the
Universidad del Paıs Vasco (UPV, 2002) for supporting
ꢀ
ꢀ
this work. Y. Lopez thanks the Gobierno Vasco (Vito-
ria) for a predoctoral fellowship and J. M. de los Santos
thanks the MCYT (Madrid) for financial support from
ꢀ
the Ramon y Cajal Program.
14. For recent contributions, see: (a) Chen, X.; Wiemer, D. F.
J. Org. Chem. 2003, 68, 6108–6114; (b) Palacios, F.;
Aparicio, D.; Ochoa de Retana, A. M.; de los Santos, J.
References and notes
ꢀ
M.; Gil, J. I.; Lopez de Munain, R. Tetrahedron:
Asymmetry 2003, 14, 689–700; (c) Davis, F. A.; Wu, Y.;
Yan, H.; McCoul, W.; Prasad, K. R. J. Org. Chem. 2003,
68, 2410–2419.
1. For reviews, see: (a) Attanasi, O. A.; Filippone, P. Synlett
1997, 1128–1140; (b) Schantl, J. G. In Houben-Weyl.
Methoden der Organische Chemie; Kropf, H., Schaumann,
E. , Eds.; Thieme: Stuttgart, 1990; Vol. E15, p 909.
2. For recent contributions, see: (a) Attanasi, O. A.; De
Crescentini, L.; Favi, G.; Filippone, P.; Giorgi, G.;
Mantenilli, F.; Santeusanio, S. J. Org. Chem. 2003, 68,
1947–1953; (b) Rossi, E.; Arcadi, A.; Abbiati, G.; Atta-
nasi, O. A.; De Crescentini, L. Angew. Chem. Int. Ed.
2002, 41, 1400–1402; (c) Avalos, M.; Babiano, R.; Cintas,
15. (a) Smith, A. B.; Yager, K. M.; Taylor, C. M. J. Am.
Chem. Soc. 1995, 117, 10879–10888; (b) Hirschmann, R.;
Smith, A. B.; Taylor, C. M.; Benkovic, P. A.; Taylor, S.
D.; Yager, K. M.; Spengler, P. A.; Benkovic, S. J. Science
1994, 265, 234–237; (c) Meyer, J. H.; Bartlett, P. A. J. Am.
Chem. Soc. 1998, 120, 4600–4609; (d) Georgiadis, D.;
Dive, V.; Yiotakis, A. J. Org. Chem. 2001, 66, 6604–6610.
16. ())-Menthyl carbazate was prepared by addition of a
solution of ())-menthyl chloroformate in dichloromethane
to a solution of hydrazine hydrate in dichloromethane in
the presence of CCl4, K2CO3 and triethylbenzylammo-
nium chloride.
17. General procedure for 5: to a room temperature solution
of chlorohydrazone 4 (5.00 mmol) in dry CH2Cl2 (25 mL),
triethylamine (0.85 mL, 6.00 mmol) was added dropwise
under a nitrogen atmosphere. The mixture was stirred at
this temperature for 45 min. The crude mixture was diluted
ꢀ
P.; Clemente, F. R.; Gordillo, R.; Jimenez, J. L.; Palacios,
J. C. J. Org. Chem. 2002, 67, 2241–2251.
3. (a) Attanasi, O. A.; De Crescentini, L.; Favi, G.;
Filippone, P.; Mantenilli, F.; Santeusanio, S. J. Org.
Chem. 2002, 67, 8178–8181, and references therein cited;
(b) Avalos, M.; Babiano, R.; Cintas, P.; Clemente, F. R.;
ꢀ
Gordillo, R.; Jimenez, J. L.; Palacios, J. C. J. Org. Chem.
2001, 66, 5139–5145, and references therein cited.
4. (a) Ferguson, G.; Lough, A. J.; Mackay, D.; Weeratunga,
G. J. Chem. Soc. Perkin Trans. I 1991, 3361–3369; (b)
Clarke, S. J.; Gilchrist, T. L.; Lemos, A.; Roberts, T. G.
Tetrahedron 1991, 47, 5615–5624; (c) Schantl, J. G.;
Nadenik, P. Synlett 1998, 786–788; (d) South, M. S.;
Jakuboski, T. L.; Westmeyer, M. D.; Dukesherer, D. R.
J. Org. Chem. 1996, 61, 8921–8934; (e) Sommer, S.
Tetrahedron Lett. 1977, 1, 117–120.
withCH Cl2 (20 mL), washed with H2O (2 · 20 mL) and
2
the aqueous phase was extracted twice with CH2Cl2
(10 mL). The solvent was dried over MgSO4 and evapo-
rated under vacuum. Diaza-alkenes 5 proved to be
unstable to chromatography and was then used in the
next steps without further purification. The identity of
products 5 was confirmed by NMR data.
5. Palacios, F.; Aparicio, D.; de los Santos, J. M. Tetrahe-
dron 1999, 55, 13767–13778.
18. (a) Attanasi, O. A.; De Crescentini, L.; Filippone, P.;
Mantenilli, F.; Santeusanio, S. Synlett 2003, 1183–1185;
(b) Abbiati, G.; Arcadi, A.; Attanasi, O. A.; De Crescen-
tini, L.; Rossi, E. Tetrahedron 2001, 57, 2031–2038;
(c) Bozzini, S.; Feluga, G.; Nardin, A.; Pizzolini, G.;
Pitacco, E.; Valentin, E. J. Chem. Soc. Perkin Trans. I
1996, 1961–1969.
6. For reviews, see: (a) Kafarski, P.; Lejezak, B. Phosphorus
Sulfur 1991, 63, 193–215; (b) Hoagland, R. E. In Biolog-
ically Active Natural Products; Culter, H. G., Ed.;
ACS Symposium Series; American Chemical Society:
Washington DC, 1988; Vol. 380, p 182.
7. Only the preparation and some reactions of chiral aza-
alkene containing a carbohydrate template in C-4 has been
described.2c;3b
19. Diastereoisomeric excess were measured by 31P NMR on
the crude reaction mixture.
20. General procedure for the addition of amine derivatives to
azo-alkenes 5: to a stirred solution of chlorohydrazone 4
(1.00 mmol) in CH2Cl2 (5 mL), Et3N (0.21 mL, 1.50 mmol)
was added at room temperature and under nitrogen
atmosphere. The mixture was stirred at room temperature
ꢀ
8. (a) Palacios, F.; Herran, E.; Rubiales, G. J. Org. Chem.
2002, 67, 2131–2135; (b) Palacios, F.; Alonso, C.; Amezua,
P.; Rubiales, G. J. Org. Chem. 2002, 67, 1941–1946.
9. (a) Palacios, F.; Oyarzabal, J.; Pascual, S.; Ochoa de
Retana, A. M. Org. Lett. 2002, 4, 769–772; (b) Palacios,
F.; Ochoa de Retana, A. M.; Pascual, S.; Oyarzabal, J.
Tetrahedron. Lett. 2002, 43, 5917–5919.
10. (a) Palacios, F.; Aparicio, D.; de los Santos, J. M.;
Vicario, J. Tetrahedron 2001, 57, 1961–1972; (b) Palacios,
F.; Aparicio, D.; Ochoa de Retana, A. M.; de los Santos,
for 15–45 min and
a solution of primary amine
(1.20 mmol) in CH2Cl2 (5 mL) was then added at the same
temperature. The reaction mixture was stirred at room
temperature for 20–120 min. The crude mixture was
diluted withCH 2Cl2 (10 mL), washed with H2O (2 · 5 mL)
and the aqueous phase was extracted twice with CH2Cl2
(5 mL). The organic layer was dried over MgSO4 and
evaporated under vacuum and the crude product was
purified by flash-chromatography (silica gel). The identity
of products 6–12 was confirmed by NMR data, IR, MS
and elemental analyses.
ꢀ
J. M.; Garcıa, J.; Oyarzabal, J. Tetrahedron 1999, 55,
3105–3116; (c) Palacios, F.; Aparicio, D.; de los Santos, J.
M. Tetrahedron 1994, 50, 12727–12742.
11. For excellent reviews, see: (a) Andreas, J.; Janek, C. F.;
Bettray, W.; Peters, R.; Enders, D. Tetrahedron 2002, 58,