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(a) Wamhoff, H.; Richard, G.; Stolben, S. Adv. Heterocycl.
Chem. 1995, 64, 159; (b) Barluenga, J.; Palacios, F. Org.
Prep. Proced. Int. 1991, 23, 1.
References and notes
1. For reviews, see: (a) Nicolau, K. C.; Snyder, S. A.;
Montagnon, T.; Vassilikogiannakis, G. Angew. Chem.,
Int. Ed. 2002, 41, 1669; (b) Jayakumar, S.; Ishar, M. P. S.;
Mahajan, M. P. Tetrahedron 2002, 58, 379; (c) Buonora,
P.; Olsen, J.-C.; Oh, T. Tetrahedron 2001, 57, 6099.
2. For recent contributions, see: (a) Alves, M. J.; Duraes, M.
M.; Gil, A. Tetrahedron Lett. 2003, 44, 5079; (b) Nicolau,
K. C.; Nevalainen, M.; Safina, B. S.; Zak, M.; Bulat, S.
Angew. Chem., Int. Ed. 2002, 41, 1941; (c) Moody, C. J.;
Hughes, R. A.; Thompson, S. P.; Alcaraz, L. Chem.
Commun. 2002, 1760; (d) Ntirampebura, D.; Ghosez, L.
Synthesis 2002, 2043.
3. (a) Jnoff, E.; Ghosez, L. J. Am. Chem. Soc. 1999, 121,
2617; (b) Bandini, E.; Martelli, G.; Spunta, G.; Bongini,
A.; Panunzio, M. Synlett 1999, 1735; (c) Ntirampebura,
D.; Ghosez, L. Tetrahedron Lett. 1999, 40, 7079; (d)
Bongini, A.; Panunzio, M.; Bandini, E.; Martelli, G.;
Spunta, G. J. Org. Chem. 1997, 62, 8911; (e) Ghosez, L.
Pure Appl. Chem. 1996, 68, 15.
14. C7F15CN was purchased from Lancaster, however CF3CN
was freshly prepared by dehydration of the corresponding
amide (CF3CONH2) Reisner, D. B.; Horning, E. C. Org.
Synth. Coll. Vol. IV 1963, 144.
15. General procedure for preparation of phosphazenes 4. A
solution 1.6 M solution of methyllithium in ether
(3.125 mL, 5 mmol) was added dropwise to a solution of
2.40 g (5 mmol) of benzyltriphenylphosphonium iodide in
ether (20 mL) cooled to 0 °C under N2. The clear red
solution was heated to reflux for 1 h. Fluoroalkylated
nitrile was added dropwise or bubbled to the ylide solution
at 0 °C and the mixture was stirred at room temperature
overnight. Selected data: compound 4a: IR (KBr) m 1600,
1341/cm; 1H NMR (400 MHz, CDCl3)
d 5.70 (d,
J ¼ 3.2 Hz, 1H), 6.98–7.85 (m, 20H); 13C NMR (100 MHz,
3
3
CDCl3) d 113.8 (dd, JCP ¼ 11.3 Hz, JCF ¼ 1.7 Hz, CH@),
1
3
122.8 (dq, JCF ¼ 278.0 Hz, JCP ¼ 24.5 Hz, CF3) 125.5–
2
133.7 (m), 137.0 (q, JCF ¼ 21.4 Hz); 31P NMR (120 MHz,
CDCl3) d 7.95; 19F NMR (282 MHz, CDCl3) d )64.1; MS
(EI) m=z 447 (M+, 100). Anal. Calcd for: C27H21F3NP
(447): C, 72.48; H, 4.73; N, 3.13. Found: C, 72.02; H, 4.68;
N, 3.10.
4. (a) Organofluorine Compounds: Chemistry and Applica-
tions; Hiyama, T., Ed.; Springer: Berlin, 2000; (b) Fluorine
in Bioorganic Chemistry; Welch, J. T., Eswarakrishnan, S.,
Eds.; Wiley: New York, 1991.
16. (a) Barluenga, J.; Ferrero, M.; Ortiz, F.; Palacios, F. J.
Chem. Soc., Perkin Trans. 1 1989, 615; (b) Ciganek, E. J.
Org. Chem. 1970, 35, 3631.
5. (a) Enantiocontrolled Synthesis of Fluoro-Organic Com-
pounds: Stereochemical Challenges and Biomedical Targets;
Soloshonok, V. A., Ed.; Wiley: New York, 1999; (b)
Fluorine-Containing Amino Acids: Synthesis and Applica-
tions; Kukhar, V. P., Soloshonok, V. A., Eds.; Wiley: New
York, 1995.
6. (a) Hou, Y.; Higashiya, S.; Fuchigami, T. J. Org. Chem.
1997, 62, 8773; (b) Hou, Y.; Higashiya, S.; Fuchigami, T.
Synlett 1997, 655.
7. (a) Ichikawa, J.; Wada, Y.; Miyazaki, H.; Mori, T.;
Kuroki, H. Org. Lett. 2003, 5, 1455; (b) Shen, Y.; Zhang,
Y.; Sun, J. J. Fluorine Chem. 2002, 116, 157; (c) Peng, W.;
Zhu, S. J. Chem. Soc., Perkin Trans. 1 2001, 3204.
8. (a) Oesterle, T.; Simchen, G. Synthesis 1985, 403; (b)
Burger, K.; Dirsteiner, G.; Fehn, J. Liebigs Ann. Chem.
1971, 747, 45; (c) Ono, T.; Kukhar, V. P.; Soloshonok, V.
A. J. Org. Chem. 1996, 61, 6563.
1
17. In the H NMR spectrum of crude reaction of compound
6a the olefinic hydrogen appeared as a singlet at d
6.90 ppm and the iminic hydrogen as a quadruplet at d
5
7.82 ppm with coupling constant of JFH ¼ 1.2 Hz.
18. Ylides and imines of phosphorus; Johnson, A. W., Kaska,
W. S., Starzewski, K. A. O., Dixon, D. A., Eds.; Wiley:
New York, 1993.
19. For preparation of ylide 8, see: Tsunoda, T.; Nagino, C.;
^
Oguri, M.; Ito, S. Tetrahedron Lett. 1996, 37, 2459.
20. (a) Coffey, D. S.; Kolis, S. P.; May, S. A. In Progress in
Heterocyclic Chemistry; Gribble, G. W., Gilchrist, T. L.,
Eds.; Pergamon: Amsterdam, 2002; Vol. 14, Chapter 6.1;
(b) Bentley, K. W. The isoquinoline Alkaloids; Harwood
Academic: Amsterdam, 1998; (c) Ciufolini, M. A. In
Advances in Heterocyclic Natural Product Synthesis; Pear-
son, W. H., Ed.; JAI: London, 1996; Vol. 3; (d) Yates, F.
S. In Comprehensive Heterocyclic Chemistry; Katritzky, A.
R., Rees, C. W., Eds.; Pergamon: New York, 1984; Vol. 2.
Chapter 2.09.
€
9. (a) Simchen, G.; Purkner, E. Synthesis 1990, 525; (b)
Burger, K.; George, G.; Fehn, J. Liebigs Ann. Chem. 1972,
757, 1; (c) Burger, K.; Fehn, J. Liebigs Ann. Chem. 1972,
757, 14; (d) Burger, K.; Meffert, A. Liebigs Ann. Chem.
1975, 316.
21. (a) Dai, G.; Larock, R. C. J. Org. Chem. 2002, 67, 7042;
(b) Huang, Q.; Hunter, J. A.; Larock, R. C. J. Org. Chem.
2002, 67, 3437.
22. General procedure for [4+2] cycloaddition reactions.
Enamine 10 (1.5 mmol) was added to a 0–10 °C solution
of azadiene 6 (1.5 mmol) in CHCl3 or toluene under N2,
and the mixture was stirred at adequate temperature, until
TLC indicated the disappearance of azadiene.
ꢀ
10. (a) Palacios, F.; Ochoa de Retana, A. M.; Martınez de
Marigorta, E.; Rodrıguez, M.; Pagalday, J. Tetrahedron
ꢀ
ꢀ
2003, 59, 2617; (b) Palacios, F.; Gil, M. J.; Martınez de
Marigorta, E.; Rodrıguez, M. Tetrahedron Lett. 1999, 40,
ꢀ
2411.
11. (a) Palacios, F.; Herran, E.; Rubiales, G.; Ezpeleta, J. M.
ꢀ
J. Org. Chem. 2002, 67, 2131; (b) Palacios, F.; Herran, E.;
Rubiales, G. J. Org. Chem. 1999, 64, 6239.
ꢀ
23. (a) Cooke, J. W. B.; Coleman, M. J.; Caine, D. M.;
Jenkins, K. P. Tetrahedron Lett. 1998, 39, 7965; (b)
Katsuyama, I.; Ogawa, S.; Yamaguchi, Y.; Funabiki, K.;
Matsui, M.; Muramatsu, H.; Shibata, K. Synthesis 1997,
1321.
12. (a) Palacios, F.; Alonso, C.; Amezua, P.; Rubiales, G. J.
Org. Chem. 2002, 67, 1941; (b) Palacios, F.; Alonso, C.;
Rubiales, G. J. Org. Chem. 1997, 62, 1146.
13. Aza-Wittig reaction affords an excellent strategy for the
construction of the C@N double bonds. For reviews, see: