A. S. Golubev et al. / Tetrahedron Letters 45 (2004) 1445–1447
1447
2226–2231; (g) Skiles, J. W.; Giannousis, P. P.; Fales,
K. R. Bioorg. Med. Chem. Lett. 1996, 6, 963–966.
Methods for Organic Synthesis with Diazo Compounds.
From Cyclopropanes to Ylides; Wiley: New York, 1998.
2. (a) Letavic, M. A.; Axt, M. Z.; Barberia, J. T.; Carty, T. J.;
Danley, D. E.; Geoghegan, K. F.; Halim, N. S.; Hoth, L.
R.; Kamath, A. V.; Laird, E. R.; Lopresti-Morrow, L. L.;
McClure, K. F.; Mitchell, P. G.; Natarajan, V.; Noe, M.
C.; Pandit, J.; Reeves, L.; Schulte, G. K.; Snow, S. L.;
Sweeney, F. J.; Tan, D. H.; Yu, C. H. Bioorg. Med. Chem.
Lett. 2002, 12, 1387–1390; (b) Lau, J. F.; Hansen, T. K.;
Kilburn, J. P.; Frydenvang, K.; Holsworth, D. D.; Ge, Y.;
Uyeda, R. T.; Judge, L. M.; Andersen, H. S. Tetrahedron
2002, 58, 7339–7344; (c) Cossy, J.; Belotti, D. Bioorg. Med.
Chem. Lett. 2001, 11, 1989–1992; (d) Beaulieu, P. L.;
Anderson, P. C.; Cameron, D. R.; Croteau, G.; Gorys, V.;
Grand-Maitre, C.; Lamarre, D.; Liard, F.; Paris, W.;
Plamondon, L.; Soucy, F.; Thibeault, D.; Wernic, D.;
Yoakim, C.; Pav, S.; Tong, L. J. Med. Chem. 2000, 43,
1094–1108; (e) Ornstein, P. L.; Arnold, M. B.; Lunn, W.
H. W.; Heinz, L. J.; Leander, J. D.; Lodge, D.; Schoepp,
D. D. Bioorg. Med. Chem. Lett. 1998, 8, 389–394; (f)
Lamarre, D.; Croteau, G.; Bourgon, L.; Thibeault, D.;
Wardrop, E.; Clouette, C.; Vaillancourt, M.; Cohen, E.;
Pargelis, C.; Yoakim, C.; Anderson, P. C. Antimicrob.
Agents Chemother. 1997, 41, 965–971.
15. Compound 6: colourless crystals; mp 34–35 °C;
22
½a ¼ )14.9 (c 1 , CHCl2); IR (KBr): m 1842 cmÀ1
;
1H
2
D
NMR (600 MHz, CDCl3): d 1.84 (1H, br m, CH2CHN),
1.90 (1H, m, CH2CH2CHN), 2.20 (1H, br m, CH2CHN),
2.41H(1, m,
C
H2CH2CHN), 3.11 (1H, br dd,
3JHF ¼ 26:1Hz, 2J ¼ 12:4 Hz, CH2N), 3.62 (1H, br d,
3J ¼ 10:5 Hz, CHN), 3.68 (1H, br t, JHF;HH ¼ 11:6 Hz,
CH2N); 13C NMR (151 MHz, CDCl3):
d 23.75 (d,
3JCF ¼ 10:3 Hz, CH2CHN), 31.81 (dd, JCF ¼ 25:9 Hz,
2JCF ¼ 23:9 Hz, CH2CH2CHN), 50.77 (dd, 2JCF ¼ 38:8 Hz,
2JCF ¼ 27:1Hz, CH2N), 55.14 (CHN), 88.06 (dqq,
2
2JCF ¼ 34:4 Hz, JCF ¼ 32:4 Hz, JCF ¼ 2:0 Hz, C(CF3)2),
2
4
1
1
5
117.62 (ddq, JCF ¼ 247:9 Hz, JCF ¼ 241:9 Hz, JCF
¼
1
3
1Hz, CF2), 120.20 (qq, JCF ¼ 287:1Hz, JCF ¼ 1Hz,
1
CF3), 121.65 (q, JCF ¼ 293:7 Hz, CF3), 166.90 (d,
5JCF ¼ 1:8 Hz, C@O); 19F NMR (376 MHz, CDCl3 with-
out 1H decoupling): d À 75:62 (q, JFF ¼ 8:4 Hz, CF3),
4
4
6
)78.73 (dq, JFF ¼ 8:4 Hz, JFF ¼ 1:2 Hz, CF3), )102.86
2
2
(d, JFF ¼ 244:6 Hz, CF2), )104.40 (dq, JFF ¼ 244:6 Hz,
6JFF ¼ 1:2 Hz, CF2); MS (EI) m=z (%): 313 [M]þ (6), 266
(9), 244 (20), 216 (100), 196 (13), 176 (7), 100 (10), 69
(20).
3. Burger, K.; Rudolph, M.; Fehn, S.; Sewald, N. J. Fluorine
Chem. 1994, 66, 87–90.
4. Golubev, A. S.; Schedel, H.; Radics, G.; Sieler, J.; Burger,
K. Tetrahedron Lett. 2001, 42, 7941–7944.
5. (a) Fischer, G. Chem. Soc. Rev. 2000, 29, 119–127; (b)
16. (a) Hudlicky, M. Org. React. 1988, 34, 513–637; (b)
Chemistry of Organic Fluorine Compounds; Hudlicky, M.,
Pavlath, A. E., Eds.; ACS Monograph 187; American
Chemical Society: Washington, DC, 1995; pp 240–242.
and references cited therein.
€
Maison, W.; Lutzen, A.; Kosten, M.; Schlemminger, I.;
17. 5,5-Difluoro-(S)-pipecolic acid 7: white powder; mp
22
D
Westerhoff, O.; Saak, W.; Martens, J. J. Chem. Soc.,
Perkin Trans. 1 2000, 1867–1871; (c) Wu, W.-J.; Raleigh,
D. P. J. Org. Chem. 1998, 63, 6689–6698; (d) Kern, D.;
Schutkowski, M.; Drakenberg, T. J. Am. Chem. Soc. 1997,
119, 8403–8408.
250 °C (sealed tube); ½a ¼ )9 (c 1 , HO); 1H NMR
2
(300 MHz, D2O): d 1.85–2.32 (m, 4H), 3.38 (ddd, J ¼ 23:5,
13.5, 5.5 Hz, 1H), 3.58 (m, 1H), 3.72 (dd, J ¼ 10:7, 2.8 Hz,
1H); 13C NMR (50.3 MHz, D2O): d 25.30 (t, J ¼ 5 Hz),
32.38 (t, J ¼ 23 Hz), 48.55 (t, J ¼ 32 Hz), 59.86, 120.92 (t,
J ¼ 242 Hz), 174.88 (t, J ¼ 5 Hz).
6. (a) Renner, C.; Alefelder, S.; Bae, J. H.; Budisa, N.;
Huber, R.; Moroder, L. Angew. Chem. 2001, 113, 949–
951; (b) Eberhardt, E. S.; Panasik, N., Jr.; Raines, R. T.
J. Am. Chem. Soc. 1996, 118, 12261–12266.
18. Zaidlewicz, M.; Brown, H. C. In Encyclopedia of Reagents
for Organic Synthesis; Paquette, L. A., Ed.; Wiley:
Chichester, 1995; pp 638–644.
7. (a) See Ref. 2a; (b) Adams, D. R.; Bailey, P. D.; Collier,
I. D.; Heffernan, J. D.; Stokes, S. J. Chem. Soc., Chem.
Commun. 1996, 349–350; (c) Baldwin, J. E.; Adlington,
R. M.; Godfrey, C. R. A.; Gollins, D. W.; Vaughan, J. G.
J. Chem. Soc., Chem. Commun. 1993, 1434–1435.
8. (a) Marin, J.; Didierjean, C.; Aubry, A.; Briand, J.-P.;
Guichard, G. J. Org. Chem. 2002, 67, 8440–8449; (b)
Hoarau, S.; Fauchere, J. L.; Pappalardo, L.; Roumestant,
M. L.; Viallefont, P. Tetrahedron: Asymmetry 1996, 7,
2585–2593; (c) Herdeis, C.; Heller, E. Tetrahedron: Asym-
metry 1993, 4, 2085–2094; (d) Bailey, P. D.; Bryans, J. S.
Tetrahedron Lett. 1988, 29, 2231–2234.
9. (a) Davis, A. F.; Yang, B.; Deng, J. J. Org. Chem. 2003,
68, 5147–5152; (b) Burger, K.; Rudolph, M.; Fehn, S.
Angew. Chem., Int. Ed. Engl. 1993, 32, 285–287.
10. Weygand, F.; Burger, K.; Engelhardt, K. Chem. Ber. 1966,
99, 1461–1469.
11. (a) Golubev, A. S.; Sewald, N.; Burger, K. Tetrahedron
19. (a) Fehn, S.; Burger, K. Tetrahedron: Asymmetry 1997, 8,
2001–2004; (b) See Ref. 9b.
20. Dmowski, W. Replacement of Oxygen by Fluorine. In
Chemistry of Organic Fluorine Compounds II, A Critical
Review; Hudlicky, M., Pavlath, A. E., Eds.; ACS Mono-
graph 187; American Chemical Society: Washington, DC,
1995; p 213.
22
D
21. Compound 10: colourless crystals; mp 51 °C, ½a ¼ )9 (c
1
1, CHCl3); H NMR (600 MHz, CDCl3): d 1.62 (1H, m,
CH2CH2CHN), 1.92 (1H, m, CH2CHN), 2.04 (1H, m,
CH2CHN), 2.33 (1H, m, CH2CH2CHN), 3.03 (1H, br dd,
J ¼ 13:4 Hz, JHF ¼ 35:5 Hz, CH2N), 3.54 (1H, br d,
J ¼ 11:5 Hz, CHN), 3.72 (1H, br t, J ¼ 12:7 Hz, CH2N),
4.78 (1H, br d, JHF ¼ 45:9 Hz, CHF); 13C NMR
(151 MHz, CDCl3):
d 22.02 (CH2CHN), 28.18 (d,
2
2JCF ¼ 22:2 Hz, CH2CH2CHN), 49.02 (d, JCF ¼ 20:8 Hz,
1
CH2N), 55.55 (CHN), 83.65 (d, JCF ¼ 179:2 Hz, CHF),
2
2
88.78 (qq, JCF ¼ 33:5 Hz, JCF ¼ 31:3 Hz, C(CF3)2),
120.28 (qq, 1JCF ¼ 287:1Hz, CF 3), 121.83 (q,
1JCF ¼ 294:2 Hz, CF3), 168.27 (C@O); 19F NMR
€
1996, 52, 14757–14776; (b) Bottcher, C.; Burger, K.
Tetrahedron Lett. 2003, 44, 4223–4226.
1
€
12. Pumpor, K.; Bottcher, C.; Fehn, S.; Burger, K. Hetero-
cycles 2003, 61, 259–269.
(376 MHz, CDCl3 without H decoupling): d À 75:28 (br
4
4
q, JFF ¼ 8 Hz, CF3), )78.68 (br dq, JFF ¼ 8:4 Hz,
2
13. Ko, K.-Y.; Lee, K.-I.; Kim, W.-J. Tetrahedron Lett. 1992,
33, 6651–6652.
14. (a) Doyle, M. P. Chem. Rev. 1986, 86, 919–939; (b) Doyle,
M. P.; Mc Kervey, M. A.; Ye, T. Modern Catalytic
6JFF ¼ 1:3 Hz, CF3), )187.24 (br dttq, JHF ¼ 45:3 Hz,
3JHF ¼ 34:3 Hz, 3JHF ¼ 11:0 Hz, 6JFF ¼ 1:3 Hz, CHF); MS
(EI) m=z (%): 295 (7) [M]þ, 198 (25) [M)CF3CO]þ, 1 69
(15), 149 (14), 102 (82), 82 (36), 69 (62).