2748
T. Konno et al. / Tetrahedron: Asymmetry 12 (2001) 2743–2748
4.51 (2H, s), 4.68 (1H, dd, J=4.5, 9.5 Hz), 5.13 (1H, d,
J=9.5 Hz), 5.67 (1H, dd, J=9.5, 15.5 Hz), 5.94 (1H,
dt, J=4.5, 15.5 Hz), 7.26–7.35 (5H, m); 13C NMR l
28.18, 49.20 (q, J=26.7 Hz), 52.68, 68.41, 72.15, 80.61,
121.37, 127.69, 127.75, 128.39, 129.80 (q, J=268.7 Hz),
135.70, 137.90, 155.11, 170.15; 19F NMR l 8.40 (3F, d,
J=11.0 Hz); IR (neat) w 1720 cm−1.
(b) Cramer, U.; Rehfeldt, A. G.; Spener, F. Biochemistry
1980, 19, 3074; (c) Johnson, M.; Raines, R.; Chang, M.;
Esaki, N.; Soda, K.; Walsh, C. Biochemistry 1981, 20,
4325; (d) Tsubotani, S.; Funabashi, Y.; Takamoto, M.;
Hakoda, S.; Harada, S. Tetrahedron 1991, 47, 8079.
3. (a) Bartlett, P. A.; Tanzella, D. J.; Barstow, J. F. Tetra-
hedron Lett. 1982, 23, 619; (b) Ohfune, Y.; Kurokawa, N.
Tetrahedron Lett. 1985, 26, 5307; (c) Kurokawa, N.;
Ohfune, Y. J. Am. Chem. Soc. 1986, 108, 6041; (d)
Baumann, H.; Duthaler, R. O. Helv. Chim. Acta 1988,
71, 1025; (e) Broxterman, Q. B.; Kaptein, B.; Kamphuis,
J.; Shoemaker, H. E. J. Org. Chem. 1992, 57, 6286.
4. Konno, T.; Ishihara, T.; Yamanaka, H. Tetrahedron Lett.
2000, 41, 8467.
5. (a) Konno, T.; Nakano, H.; Kitazume, T. J. Fluorine
Chem. 1997, 86, 81; (b) Konno, T.; Kitazume, T. Tetra-
hedron: Asymmetry 1997, 8, 223; (c) Konno, T.; Umetani,
H.; Kitazume, T. J. Org. Chem. 1997, 62, 137; (d) Konno,
T.; Kitazume, T. Chem. Commun. 1996, 2227.
6. (a) Abe, H.; Nitta, H.; Mori, A.; Inoue, S. Chem. Lett.
1992, 2443; (b) Danichefsky, S. J.; Cabal, M. P.; Chow,
K. J. Am. Chem. Soc. 1989, 111, 3456; (c) Grieco, P. A.;
Tanigawa, T.; Bongers, S. L.; Tanaka, H. J. Am. Chem.
Soc. 1980, 10, 7587.
4.4.4. Methyl 2-(t-butoxycarbamoyl)-3-difluoromethyl-
1
(4E)-undecenoate (2S,3R)-syn-9d. Yield 53%. H NMR
l 0.87 (3H, t, J=7.0 Hz), 1.25–1.37 (8H, m), 1.44 (9H,
s), 2.04 (2H, q, J=7.0 Hz), 2.89 (1H, m), 3.74 (3H, s),
4.55 (1H, m), 5.09 (1H, d, J=7.5 Hz), 5.23 (1H, dd,
J=9.5, 15.5 Hz), 5.71 (1H, dt, J=7.00, 15.5 Hz), 5.86
(1H, dt, J=4.5, 56.0 Hz); 13C NMR l 14.02, 22.54,
28.20, 28.66, 28.80, 31.59, 32.61, 49.94 (t, J=86.8 Hz),
52.38, 53.06, 80.35, 115.94 (t, J=251.5 Hz), 119.54,
139.49, 155.08, 171.00; 19F NMR l −46.95 (dd, J=15.4,
56.0 Hz); IR (neat) w 1720 cm−1; MS (CI) m/z (rel.
intensity) 364 (M+H, 3), 308 (100). HRMS (CI) calcd
for C18H32F2NO4 m/z 364.2300. Found 364.2287;
[h]2D2=+5.3 (c 1.1, CHCl3).
4.4.5. Methyl 2-(t-butoxycarbamoyl)-3-pentafluoroethyl-
(4E)-undecenoate (2S*,3R*)-syn-9e. Yield 62%. 1H
NMR l 0.87 (3H, t, J=7.0 Hz), 1.26–1.38 (8H, m),
1.45 (9H, s), 2.06 (2H, q, J=7.00 Hz), 3.33 (1H, m),
3.75 (3H, s), 4.68 (1H, dd, J=5.5, 9.5 Hz), 5.09 (1H, d,
J=9.0 Hz), 5.30 (1H, dd, J=5.5, 9.5 Hz), 5.75 (1H, dt,
J=7.0, 15.0 Hz); 13C NMR l 14.00, 22.53, 28.19, 28.62,
31.58, 32.42, 47.27 (t, J=20.3 Hz), 52.54, 52.81, 80.48,
114.10–122.15 (m), 118.39, 140.33, 154.94, 170.40; 19F
NMR l −7.09 (3F, s), −42.90 (2F, dq, J=25.3, 270.6
Hz); IR (neat) w 1724 cm−1; MS (CI) m/z (rel. intensity)
432 (M+H, 7), 376 (100); HRMS (CI) calcd for
C19H31F5NO4 m/z 432.2174. Found 432.2157.
7. (a) Sakaguchi, K.; Suzuki, H.; Ohfune, Y. Chirality 2001,
357; (b) Pereira, S.; Srebnik, M. Aldrichim. Acta 1993, 26,
17; (c) Wipf, P. In Comprehensive Organic Synthesis;
Trost, B. M., Fleming, I., Eds.; Oxford, 1991; Vol. 7,
Chapter 7.2.
8. Bartlett, P. A.; Barstow, J. F. J. Org. Chem. 1982, 47,
3933.
9. In contrast to our method using mesylates possessing the
chirality in the allylic part, Kazmaier et al. have suc-
ceeded in the stereoselective rearrangement using allyl
esters with the stereogenic center in the amino acids part.
See (a) Kazmaier, U.; Maier, S. Chem. Commun. 1998,
2535; (b) Kazmaier, U. Liebigs Ann./Recl. 1997, 285; (c)
Kazmaier, U. J. Org. Chem. 1996, 61, 39; (d) Kazmaier,
U. Synlett 1995, 1138; (e) Kazmaier, U. Angew. Chem.,
Int. Ed. Engl. 1994, 33, 998; (f) Kazmaier, U. Tetrahedron
1994, 50, 12895.
10. Bott, G.; Field, F. G.; Sternhell, S. J. Am. Chem. Soc.
1980, 102, 5618.
11. Ramachandran, P. V.; Gong, B.; Teodorovic, A. V.;
Brown, H. C. Tetrahedron: Asymmetry 1992, 3, 1089.
12. Dale, J. A.; Dull, D. L.; Mosher, H. S. J. Org. Chem.
1969, 34, 1316.
References
1. (a) Kukhar, V. P.; Soloshonok, V. A. Fluorine-containing
Amino Acids; John Wiley and Sons: New York, 1995; (b)
Ojima, I.; McCarthy, J. R.; Welch, J. T. Biomedical
Frontiers of Fluorine Chemistry; ACS Books, Eds.; Amer-
ican Chemical Society: Washington, DC, 1996; (c) Abe,
H.; Amii, H.; Uneyama, K. Org. Lett. 2001, 3, 313; (d)
Percy, J. M.; Prime, M. E.; Broadhurst, M. J. J. Org.
Chem. 1998, 63, 8049; (e) Soloshonok, V. A.; Avilov, D.
V.; Kukhar, V. P.; Meervelt, L. V.; Mischenko, N. Tetra-
hedron Lett. 1997, 38, 4903; (f) Tsukamoto, T.; Coward,
J. K. J. Org. Chem. 1996, 61, 2497; (g) Hart, B. P.; Haile,
W. H.; Licato, N. J.; Bolanowska, W. E.; McGuire, J. J.;
Coward, J. K. J. Med. Chem. 1996, 39, 56.
13. Getef, G.; Laurent, A. J.; Laurent, E. G. J. Fluorine
Chem. 1996, 80, 27.
14. In the previous communication, it has been proven by the
chemical method that the allylic substitution reaction
proceeded with retention of configuration at the stereo-
center. See Ref. 4.
2. (a) Katagiri, K.; Tori, K.; Kimura, Y.; Yoshida, T.;
15. Trost, B. M. Acc. Chem. Res. 1980, 13, 385.
Nagasaki, T.; Minato, H. J. Med. Chem. 1967, 10, 1149;