8870
J. Mulzer et al. /Tetrahedron Letters 45 (2004) 8867–8870
4. Okude, Y.; Hiyama, T.; Nozaki, H. Tetrahedron Lett.
1. Experimental
1977, 18, 3829; Sustmann, R.; Altevogt, R. Tetrahedron
Lett. 1981, 22, 5167.
5. Colorless crystals (mp 95°C). H NMR (CDCl3): d 0.66
A suspension of anhydrous chromium(III)chloride
(27mmol) in THF (100mL) was treated under vigorous
stirring at 0°C with lithium aluminumhydride
(13.5mmol) in small portions. After the evolution of
hydrogen has ceased the mixture was stirred for
additional 20min at ambient temperature. Then the
mixture was cooled to 0°C and the aldehyde (15mmol)
and the allylic bromide (10mmol) in THF (20mL each)
were added dropwise in succession and the mixture
was stirred at room temperature for 36h. Then the
reaction was quenched with saturated aqueous sodium
hydroxide (15mL) and solid sodium sulfate (20g) was
added. The mixture was filtered over Celite, dried over
sodium sulfate, concentrated under reduced pressure,
and purified by column chromatography (silicagel,
hexane–ethylacetate) or HPLC (0.8% 1-propanol in
hexane).
1
and 0.71 (d, 6H, J = 7.5Hz), 0.92 and 0.95 (ddd, 2H,
J = 13Hz, J = 7.5Hz, 2H), 1.41 and 1.42 (dddq, 2H,
J = 8Hz, J = 7.5Hz), 1.50 and 1.56 (ddd, 2H, J = 13Hz,
J = 9Hz, J = 8Hz), 1.87 and 2.01 (mc, 1H), 1.99 and 2.16
(mc, 2H), 3.33 and 3.40 (dd, 2H, J = 8Hz, J = 7Hz), 3.45
and 3.84(dd, 2H,
J = 13Hz, J = 5Hz), AB-system
(dA = 4.21, dB = 4.33, JAB = 12Hz, 2H), AB-system
(dA = 4.35, dB = 4.44, JAB = 12Hz, 2H), 4.90 and 5.00
(dd, 2H, J = 10Hz, J = 2Hz), 5.00 (2dd, 2H, J = 17Hz,
J = 2Hz), 5.40 and 5.50 (ddd, 2H, J = 17Hz, J = 10Hz,
J = 9Hz), 7.31 (mc, 10H). 13C NMR (CDCI3): d 15.17,
15.28, 34.26, 34.70, 37.46, 39.84, 42.34, 45.01, 45.79, 48.88,
50.26, 50.62, 71.04, 71.33, 82.88, 84.89, 112.75, 114.23,
125.89, 126.03, 126.13, 127.13, 127.27, 127.40, 127.52,
127.70, 127.83, 128.00, 128.10, 128.18, 128.25, 128.33,
128.61, 133.75, 142.46, 144.98. IR (KBr): m 3080m, 3065m,
3025s, 3020w, 2955vs, 2920vs, 2865vs, 2855vs, 1945w,
1898w, 1710m, 1635m, 1491m, 1450s, 1421w, 1400m,
1372m, 1350br m, 1295w, 1259m, 1211m, 1176m, 1153m,
1103vs, 1082s,1070s, 1028m, 999m, 906s, 821w, 788w,
753s, 703vs, 682w, 652mcmÀ1. MS (EI, 80eV, 90°C): m/e
610 (1%, M), 519 (3%, MÀC7H7), 502 (3%, MÀC7H7O),
411 (1%, MÀC7H7ÀC7H7O), 394(3%, M À2C7H7O), 305
(13%, M/2), 287 (5%), 231 (2%), 215 (3%, M/2ÀC7H7), 199
(47%, M/2ÀC7H7O), 143 (10%), 107 (22%, C7H7O), 91
(100%, C7H7). Anal. Calcd for C44H50O2: C, 86.51; H,
8.25. Found: C, 86.66, H, 8.28.
Acknowledgements
We thank Professor Dr. Christian Lehmann for per-
forming the crystal structure analysis of compound 22,
Dr. Jurgen Buschmann and Professor Dr. Peter Luger,
¨
FU Berlin for performing the one of 28a, and Dr.
Burkhard Kirste, FU Berlin for the NOE experiments
with 25.
6. For a review, see: Curran, D. P.; Porter, N. A.; Giese,
B. Stereochemistry of Radical Reactions; VCH: Wein-
heim, 1995, p 31ff; For related radical cyclizations with
Cr(II), see: Takai, K.; Nitta, K.; Fujimura, O.; Uti-
moto, K. J. Org. Chem. 1989, 54, 4732; Hackmann, C.;
Supplementary data
Supplementary data associated with this article can be
of compounds 12, 13, 17, 18, 20, 21, 25, 28a, 28b, 28c,
29c, 28d, 29d.
Scha¨fer, H. J. Tetrahedron 1993, 49, 4559; Lubbers, T.;
Scha¨fer, H. J. Synlett 1992, 743.
¨
7. Mulzer, J.; Greifenberg, S.; Beckstett, A.; Gottwald, M.
Liebigs Ann. Chem. 1992, 1131.
8. This result is contrary to the behavior of SmI2, which in
related systems induces eliminations due to the formation
of transient carbanions.2b The structure of 28a was
elucidated via single crystal diffraction.12
References and notes
9. Review on chromium-g3 complexes: Whiteley, M. N.
Abel, E. W.; Stone, F. G. A.; Wilkinson, G., Eds. in chief
In Comprehensive Organometallic Chemistry II; Labinger,
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pp 335–346.
1. (a) Okude, Y.; Hirano, S.; Hiyama, T.; Nozaki, H. J. Am.
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Kimura, K.; Nozaki, H. Bull. Chem. Soc. Jpn. 1982, 55,
561; (c) Buse, C. T.; Heathcock, C. H. Tetrahedron Lett.
1978, 19, 1685; (d) Hiyama, T.; Kimura, K.; Nozaki, H.
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Ch. E.; Jubert, C.; Knochel, P. J. Org. Chem. 1995, 60,
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12. The crystal data can be obtained free of charge via www
from the Cambridge Crystallographic Data Centre, 12
Union Road, Cambridge, CB21EZ, UK, fax: +44 1223
336 033 or deposit@ccdc.cam.uk under the registration
numbers CCDC 241179 (22) and 241180 (28a).
2762, and earlier work; (f) Furstner, A.; Shi, N. J. Am.
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G.; Melchiorre, P.; Umani-Ronchi, A. Angew. Chem., Int.
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Chem. Commun. 1993, 1654.
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L. A.; Scheid, G. Synthesis 1999, 1; Furstner, A. Chem.
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Rev. 1999, 99, 991; Semmelhack, M. F.. In Organometal-
lics in Organic Synthesis, 2nd ed.; Schlosser, M., Ed.,
Wiley: Chichester, 2000; pp 1012–1021; (b) For related
work on SmI2-reactions, see: Curran, D. P.; Fevig, T. L.;
Jasperse, C. P.; Totleben, M. J. Synlett 1992, 943.
3. Mulzer, J.; Kattner, L.; Strecker, A. R.; Schro¨der, C.;
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