2960
M. Yus et al. / Tetrahedron Letters 43 (2002) 2957–2960
In conclusion, we report in this paper the DTBB-
catalysed lithiation of 6-chloro-1-hexene and related
systems, which can be controlled either giving the corre-
sponding open-chain compounds at −78°C or the cyclic
derivatives at −30°C. We believe that in the second case
an intramolecular carbolithiation takes place trans-
forming the initially formed organolithium intermediate
into the corresponding cyclic one.28
11. For mechanistic studies, see: (a) Yus, M., Herrera, R. P.;
Guijarro, A. Tetrahedron Lett. 2001, 42, 3455; (b) Yus, M.;
Herrera, R. P.; Guijarro, A. Chem. Eur. J., submitted.
12. For a polymer supported arene-catalysed version of this
reaction, see: (a) Go´mez, C.; Ruiz, S.; Yus, M. Tetrahedron
Lett. 1998, 39, 1397–1400; (b) Go´mez, C.; Ruiz, S.; Yus,
M. Tetrahedron 1999, 55, 7017–7026; (c) Arnauld, T.;
Barrett, A. G. M.; Hopkins, B. T. Tetrahedron Lett. 2002,
43, 1081–1083.
13. Last paper on this topic from our laboratory: Yus, M.;
Ortiz, J.; Na´jera, C. ARKIVOC 2002, 2, 38–47.
14. Holy, N. J. Chem. Rev. 1974, 74, 243–277.
Acknowledgements
15. (a) For a review, see: Guijarro, D.; Yus, M. Recent Res.
Dev. Org. Chem. 1998, 2, 713–744; (b) Last paper on this
topic from our laboratory: Yus, M.; Foubelo, F.; Fer-
ra´ndez, J. V. Eur. J. Org. Chem. 2001, 2809–2813.
16. For reviews, see. (a) Na´jera, C.; Yus, M. Trends Org. Chem.
1991, 2, 155–181; (b) Na´jera, C.; Yus, M. Recent Res. Dev.
Org. Chem. 1997, 1, 67–96; (c) Yus, M.; Foubelo, F. Rev.
Heteroatom Chem. 1997, 17, 73–107; (d) Na´jera, C.; Yus,
M. Curr. Org. Chem., submitted.
17. Last paper on this topic from our laboratory: Yus, M.;
Soler, T.; Foubelo, F. J. Org. Chem. 2001, 66, 6207–6208.
18. (a) For a review, see: Foubelo, F.; Yus, M. Trends Org.
Chem. 1998, 7, 1–26; (b) Last paper on this topic from our
laboratory: Yus, M.; Mart´ınez, P.; Guijarro, D. Tetra-
hedron 2001, 57, 10119–10124.
This work was generously supported by the Direccio´n
General de Ensen˜anza Superior (DGES) of the current
Spanish Ministerio de Ciencia y Tecnolog´ıa (MCyT;
grant no. PB97-0133). R.O. thanks the MCyT for a
scholarship.
References
1. For a recent report, see: Ashweek, N. J.; Coldham, I.;
Snowden, D. J.; Vennall, G. P. Chem. Eur. J. 2002, 8,
195–207 and references cited therein.
2. Wakefield, B. J. Organolithium Methods; Academic Press:
London, 1988.
19. For a review, see: Guijarro, A.; Go´mez, C.; Yus, M. Trends
3. For recent leading references, see: (a) Norsikian, S.; Marek,
I.; Klein, S.; Poisson, J. F.; Normant, J. F. Chem. Eur. J.
1999, 5, 2055–2068; (b) Marek, I. J. Chem. Soc., Perkin
Trans. 1 1999, 535–544; (c) Norsikian, S.; Baudry, M.;
Normant, J. F. Tetrahedron Lett. 2000, 41, 6575–6578; (d)
Wei, X.; Taylor, R. J. K. Angew. Chem., Int. Ed. 2000, 39,
409–412; (e) Bailey, W. F.; Mealy, M. J. J. Am. Chem. Soc.
2000, 122, 6787–6788; (f) Gil, G. S.; Groth, U. M. J. Am.
Chem. Soc. 2000, 122, 6789–6790; (g) Krief, A.; Remacle,
B.; Mercier, J. Synlett 2000, 1443–1446; (h) Deiters, A.;
Fro¨hlich, R.; Hoppe, D. Angew. Chem., Int. Ed. 2000, 39,
2105–2107; (i) Myers, A. G.; Goldberg, S. D. Angew. Chem.,
Int. Ed. 2000, 39, 2732–2735; (j) Bre´mand, N.; Mangeney,
P.; Normant, J. F. Tetrahedron Lett. 2001, 42, 1883–1885.
4. See, for instance: (a) Bailey, W. F.; Carson, M. W. J. Org.
Chem. 1998, 63, 9960–9967; (b) Bailey, W. F.; Carson, M.
W. Tetrahedron Lett. 1999, 40, 5433–5437.
Org. Chem. 2000, 8, 65–91.
20. Last paper on this topic from our laboratory: Radivoy, G.;
Alonso, F.; Yus, M. Synthesis 2001, 427–430.
21. Lithium powder was prepared from commercially available
lithium granules (99%, high sodium content, Aldrich) using
an impact grinding mill (IKA MF 10) as it was already
described before by us (see Ref. 18b).
22. (a) Monograph: Blomberg, C. The Barbier Reaction and
Related Processes; Springer: Berlin, 1993; (b) Review:
Alonso, F.; Yus, M. Recent Res. Dev. Org. Chem. 1997,
1, 397–436.
23. Bates, R. B.; Kroposki, L. M.; Potter, D. E. J. Org. Chem.
1972, 37, 560–562.
24. Alonso, E.; Guijarro, D.; Mart´ınez, P.; Ramo´n, D. J.; Yus,
M. Tetrahedron 1999, 55, 11027–11038.
25. Yus, M.; Foubelo, F.; Ferra´ndez, J. V.; Bachki, A.
Tetrahedron, submitted.
5. (a) For a review, see: Cohen, T.; Bhupathy, M. Acc. Chem.
Res. 1989, 22, 152–161; (b) For a recent account, see: Cheng,
D.; Zhu, S.; Liu, X.; Norton, S. H.; Cohen, T. J. Am. Chem.
Soc. 1999, 121, 10241–10242.
6. (a) Screttas, C. G.; Micha-Screttas, M. J. Org. Chem. 1978,
43, 1064–1071; (b) Screttas, C. G.; Micha-Screttas, M. J.
Org. Chem. 1979, 44, 713–719.
7. See, for instance: (a) Coldham, I.; Hufton, R. Tetrahedron
1996, 52, 12541–12552; (b) Coldham, I.; Hufton, R.;
Snowden, D. J. J. Am. Chem. Soc. 1996, 118, 5322–5323.
8. Rychnovsky, S. D.; Hata, T.; Kim, A. I.; Buckmelter, A.
J. Org. Lett. 2001, 3, 807–810.
26. For a recent paper, see: Capriati, V.; Florio, S.; Ingrosso,
G.; Granito, G.; Troisi, L. Eur. J. Org. Chem. 2002, 478–484
and references cited therein.
27. Bailey, W. F.; Patricia, J. J.; DelGobbo, V. C.; Jarret, R.;
Okarma, P. J. J. Org. Chem. 1985, 50, 1999–2000.
28. Typical procedure for compounds 3 and 5: Chlorinated
compound 1 (0.138 mL, 1 mmol) was directly added over
a green suspension of Li powder (50 mg, 7 mmol) and DTBB
(26.6 mg, 0.1 mmol) in THF (3 mL) at the corresponding
temperature (−78 or −30°C). The reaction was stirred at the
same temperature for 45 min, the corresponding elec-
trophile (1.1 mmol) was then added and after 15 min stirring
the reaction crude was hydrolysed with 2 M HCl (10 mL).
The mixture was allowed to reach room temperature and
extracted with diethyl ether (3×10 mL). The organic phase
was dried over anhydrous magnesium sulphate and evap-
orated at reduced pressure to yield the title compound.
Purification by column chromatography (silica gel, hexane/
ethyl acetate) gave pure compounds 3 and 5.
9. First account from our laboratory: Yus, M.; Ramo´n, J. D.
J. Chem. Soc., Chem. Commun. 1991, 398–400.
10. Reviews on arene-catalysed lithiation: (a) Yus, M. Chem.
Soc. Rev. 1996, 25, 155–161; (b) Ramo´n, D. J.; Yus, M.
Eur. J. Org. Chem. 2000, 225–237; (c) Yus, M. Synlett 2001,
1197–1205; (d) Yus, M.; Ramo´n, D. J. Lat. Kim. Z. 2002,
in press.