M. E. Jung, J. I. Wasserman / Tetrahedron Letters 44 (2003) 7273–7275
7275
Acknowledgements
ride (Moughamir, K.; Mezgueldi, B.; Atmani, A.;
Mestdagh, H.; Rolando, C. Tetrahedron Lett. 1999, 40,
59–62).
We thank the National Institutes of Health (CA72684)
for generous financial support and the National Science
Foundation under equipment grant CHE-9974928.
9. Representative spectroscopic data for 5, 7, and 9: Com-
1
pound 5: H NMR (CDCl3, 400 MHz) l: 5.60 (dd, 1H,
J=6.7, 2.3 Hz), 4.39 (dd, 1H, J=11.4, 4.1 Hz), 2.04 (s,
3H), 1.10–2.00 (m, 9H), 1.06 (s, 3H), 0.97 (s, 3H), 0.94 (s,
3H). 13C NMR (CDCl3, 100 MHz) l: 170.6, 141.2, 121.5,
81.2, 50.4, 29.7, 38.5, 37.4, 29.1, 27.0, 24.0, 22.9, 21.2,
References
1
20.6, 13.1. Compound 7: H NMR (CDCl3, 500 MHz) l:
5.73 (dd, 1H, J=6.7, 2.1 Hz), 5.72 (m, 1H), 2.30 (dd, 1H,
J=17.0, 6.8 Hz), 2.19 (dddd, 1H, J=17.9, 5.6, 5.6, 1.5
Hz), 2.10 (m, 1H), 2.05 (m, 1H), 1.72 (m, 1H), 1.71 (m,
1H), 1.52 (m, 1H), 1.16 (s, 3H), 1.16 (s, 3H), 1.07 (s, 3H).
13C NMR (CDCl3, 125 MHz) l: 141.4, 140.9, 124.1,
121.6, 50.8, 40.4, 39.8, 38.2, 29.0, 27.0, 19.8, 19.3, 18.9.
1. Isolation of dichlorolissoclimide: (a) Malochet-Grivois,
C.; Cotelle, P.; Baird, J. F.; Henichart, J. P.; Debitus, C.;
Roussakis, C.; Verbist, J.-F. Tetrahedron Lett. 1991, 32,
6701–6702. Isolation of chlorolissoclimide: (b) Baird, J.
F.; Malochet-Grivois, C.; Roussakis, C.; Cotelle, P.;
Henichart, J. P.; Debitus, C.; Verbist, J.-F. Nat. Prod.
Lett. 1994, 4, 43–50. Crystal structure of dichlorolisso-
climide: (c) Toupet, L.; Biard, J. F.; Verbist, J.-F. J. Nat.
Prod. 1996, 59, 1203–1204. Biological Activity: (d) Rous-
sakis, C.; Charrier, J.; Riou, D.; Biard, J. F.; Malochet,
C.; Meflah, K.; Verbist, J.-F. Anti-Cancer Drug Design
1994, 9, 119–128 and references cited therein.
2. Isolation of reticulidins: (a) Wratten, S. J.; Faulkner, D.
J. Tetrahedron Lett. 1978, 16, 1395–1398; (b) Simpson, J.
S.; Raniga, P.; Garson, M. J. Tetrahedron Lett. 1997, 38,
7947–7950; (c) Tanaka, J.; Higa, T. J. Nat. Prod. 1999,
62, 1339–1340; (d) Musman, M.; Tanaka, J.; Higa, T. J.
Nat. Prod. 2001, 64, 111–113.
1
Compound 9: H NMR (CDCl3, 500 MHz) l: 5.67 (dd,
1H, J=5.0, 2.7 Hz), 4.17 (ddd, 1H, J=12.2, 11.1, 4.4
Hz), 3.69 (d, 1H, J=10.9 Hz), 2.65 (dd, 1H, J=13.5, 4.4
Hz), 2.21 (ddd, 1H, J=18.0, 5.5, 5.2 Hz), 2.12 (dddd, 1H,
18.0, 10.7. 6.4, 2.7 Hz), 1.79 (dd, 1H, J=13.3, 6.9 Hz),
1.72 (dd, 1H, J=12.9, 12.9 Hz), 1.55 (m, 1H), 1.47 (d,
1H, J=12.9 Hz), 2.00 (s, 3H), 1.18 (s, 3H), 0.99 (s, 3H).
13C NMR (CDCl3, 125 MHz) l: 140.2, 124.1, 76.8, 60.3,
52.2, 47.0, 42.0, 41.8, 29.6, 27.1, 19.7, 17.8. IR (thin film):
2975, 1644, 1467, 1395, 1381, 985, 951, 889, 845, 779
cm−1. High resolution MS (EI, m/z): 280.0547, calcd for
C13H19Cl3 280.0552.
10. Firouzabadi, H.; Shiriny, F. Tetrahedron 1996, 52,
14929–14936.
3. For a recent example, see: Uddin, M. J.; Kokubo, S.;
Ueda, K.; Suenaga, K.; Uemura, D. Chem. Lett. 2002,
10, 1028–1029 and references cited therein.
11. For
a representative mechanism see: Jung, M. E.;
Hatfield, G. L. Tetrahedron Lett. 1982, 23, 3991–3994.
12. Jung, M. E.; Gomez, A. V. Tetrahedron Lett. 1993, 34,
2891–2894.
13. For a recent discussion of the stability of halonium
cations see: Teberekidis, V. I.; Sigalas, M. P. Tetrahedron
2003, 59, 4749–4756.
4. Tungsten hexachloride has been utilized in several proce-
dures such as the dehydration of epoxides to olefins
(Umbreit, M. A.; Sharpless, K. B. Org. Synth. 1981, 60,
29–34) and more recently the chlorination of alcohols
(Coe, E. M.; Jones, C. J. Polyhedron 1992, 11, 3123–
3128). Also see Ref. 11.
14. Tordeux, M.; Boumizane, K.; Wakselman, C. J. Org.
5. Hansson, L.; Carlson, R.; Sjo¨berg, A.-L. Acta Chem.
Chem. 1993, 58, 1939–1940.
Scand. 1990, 44, 1036–1041.
15. Cuddy, B. D.; Grant, D.; Karim, A; McKervey, M. A.;
Rea, E. J. F. J. Chem. Soc., Perkin Trans. 1 1972, 21,
2701–2707.
6. Dutcher, J. S.; Macmillan, J. G.; Heathcock, C. H. J.
Org. Chem. 1976, 41, 2663–2669.
7. Representative experimental procedure: To a solution of
ketone 4 (0.126 g, 0.50 mmol) in dichloromethane (5 mL)
was added tungsten hexachloride (0.397 g, 1.00 mmol)
and the solution refluxed (45°C) for 20 min. The reaction
mixture was diluted with diethyl ether (25 mL) and
poured into 2N sodium hydroxide (15 mL). The organic
layer was washed with 2N sodium hydroxide and brine.
After drying over magnesium sulfate and filtering to
remove the drying agent, the solvent was removed in
vacuo to yield vinyl chloride 5 (0.128 g, 0.47 mmol, 94%)
as a reddish oil which solidified under vacuum. The vinyl
chlorides could be purified by careful column or thick
layer chromatography on silica gel.
16. This compound has been prepared by chlorination of
p-cymene (Tauno, K. Chemosphere 1989, 19, 1349–1356)
but never by this type of rearrangement, although
bromonitrocamphane undergoes a similar rearrangement
to give the bromo analogue. See: (a) McPhail, K. L.;
Rivett, D. E. A.; Lack, D. E.; Davies-Coleman, M. T.
Tetrahedron 2000, 56, 9391–9396; (b) Ranganathan, S.;
Raman, H. H. Tetrahedron 1974, 30, 63–72.
17. Paukstelis, J. V.; Macharia, B. W. J. Org. Chem. 1973,
38, 646–648.
18. Laihia, K.; Paasivirta, J.; Pikkarainen, H.; Aho-Pullia-
ninen, S. Org. Magn. Reson. 1984, 22, 117–119.
19. Hanson, J. R. In Wagner–Meerwein Rearrangements;
Trost, B. M.; Fleming, I., Eds.; Comp. Org. Synth.;
Pergamon, 1991; Vol. 3, Chapter 3.1, pp. 706–707.
8. The structure was also confirmed by an independent
synthesis of 5 via treatment of the corresponding known
ketoalcohol with methanesulfonic acid and acetyl chlo-