E. T. Chernick et al. / Tetrahedron Letters 42 (2001) 8575–8578
8577
2. (a) Carbon-Rich Compounds II, Top. Curr. Chem. 1999,
201; (b) Bunz, U. H. F.; Rubin, Y.; Tobe, Y. Chem. Soc.
Rev. 1999, 107–119; (c) Diederich, F.; Rubin, Y. Angew.
Chem., Int. Ed. Engl. 1992, 31, 1101–1123.
3. (a) Haley, M. M.; Wan, W. B. In Advances in Strained
and Interesting Organic Molecules; Halton, B., Ed.; JAI
Press: New York, 2000; Vol. 8, pp. 1–41; (b) Ho¨ger, S.;
Enkelmann, V.; Bonrad, K.; Tschierske, C. Angew.
Chem., Int. Ed. 2000, 39, 2268–2270; (c) Tobe, Y.; Fujii,
T.; Matsumoto, H.; Tsumuraya, K.; Noguchi, D.; Naka-
gawa, N.; Sonoda, M.; Naemura, K.; Achiba, Y.; Waka-
bayashi, T. J. Am. Chem. Soc. 2000, 122, 1762–1775; (d)
Eisler, S.; Tykwinski, R. R. Angew. Chem., Int. Ed. 1999,
38, 1940–1943.
O
O
R2
R1
a
R2
R1
Cl
TMS
R2
R2
9a R1 = t-Bu, R2 = H
9b R1 = n-Hex, R2 = H
9c R1 = R2 = OMe
10a 76%
10b 90%
10c 91%
b
Br Br
R2
4. Campbell, K.; McDonald, R.; Branda, N. R.; Tykwinski,
R. R. Org. Lett. 2001, 3, 1045–1048.
5. (a) For polydiacetylenes, see: In Polydiacetylenes; Bloor,
D.; Chance, R. R., Eds.; Martinus Nijhoff: Dordrecht,
1985; (b) Wegner, G. Makromol. Chem., Suppl. 1984, 6,
347–357.
6. Hay, A. S. J. Org. Chem. 1962, 27, 3320–3321.
7. Eglinton, G.; Galbraith, A. R. Chem. Ind. (London) 1956,
737–738.
8. For an excellent review of butadiyne formation under
both homo- and heterocoupling conditions, see: Siemsen,
P.; Livingston, R. C.; Diederich, F. Angew. Chem., Int.
Ed. 2000, 39, 2633–2657.
R2
R1
c
R1
TMS
TMS
R2
R2
12a 88%
12b 70%
12c 51%
11a 60%
11b 79%
11c 91%
Scheme 2. Reagents and conditions: (a) TMSCꢀCTMS, AlCl3,
CH2Cl2, 0 to 25°C; (b) PPh3 (2 equiv.), CBr4, CH2Cl2; (c)
n-BuLi, hexanes, −78 to −40°C.
Br
Ar
Br
9. (a) Chodkiewicz, W.; Cadiot, P. C. R. Hebd. Seances
Acad. Sci. 1955, 241, 1055–1057; (b) Chodkiewicz, W.
Ann. Chim. (Paris) 1957, 2, 819–869.
n-BuLi,
hexanes,
Ar
n-Bu
–78 to –40°C
n-Bu
10. (a) Negishi, E.; Hata, M.; Xu, C. D. Org. Lett. 2000, 2,
3687–3689; (b) Godt, A. J. Org. Chem. 1997, 62, 7471–
7474; (c) Kitamura, T.; Tanaka, T.; Taniguchi, H.; Stang,
P. J. J. Chem. Soc., Perkin Trans. 1 1991, 2892–2893; (d)
Nishihara, Y.; Ikegashira, K.; Mori, A.; Hiyama, T.
Tetrahedron Lett. 1998, 39, 4075–4078; (e) Wityak, J.;
Chan, J. B. Synth. Commun. 1991, 21, 977–979; (f) Ama-
tore, C.; Blart, E.; Geneˆt, J. P.; Jutand, A.; Lemaire-
Audoire, S.; Savignac, M. J. Org. Chem. 1995, 60,
6829–6839.
11. Sonogashira, K. In Metal-Catalyzed Cross-Coupling
Reactions; Diederich, F.; Stang, P. J., Eds.; Wiley-VCH:
Weinheim, 1997; Chapter 5.
12. (a) Fritsch, P. Liebigs Ann. Chem. 1894, 279, 319–323; (b)
Buttenberg, W. P. Liebigs Ann. Chem. 1894, 279, 324–
337; (c) Wiechell, H. Liebigs Ann. Chem. 1894, 279,
337–344.
13a Ar = 2-thienyl
14a Ar = 2-thienyl 86%
13b Ar = 3-MeO-C6H4
14b Ar = 3-MeO-C6H4 89%
Scheme 3.
In summary, the modified FBW rearrangement
described herein provides a facile route to a range of
aryl diyne systems. This synthetic route offers several
attractive features versus more commonly employed
palladium coupling methods including (1) the wide
range of commercially availability of aryl aldehydes
and carboxylic acid precursors, (2) applicability to elec-
tron-rich aryl groups, (3) generally rapid reaction times
and easy purification/isolation.27
13. For reviews, see: (a) Kirmse, W. Angew. Chem., Int. Ed.
Engl. 1997, 36, 1164–1170; (b) Stang, P. J. Chem. Rev.
1978, 78, 383–405; (c) Hartzler, H. D. In Carbenes; Moss,
R. A.; Jones, Jr., M., Eds.; Wiley and Sons: New York,
1983; Vol. 2, pp. 43–100. See also: (d) Rezaei, H.;
Yamanoi, S.; Chemla, F.; Normant, J. F. Org. Lett. 2000,
2, 419–421; (e) Mourie`s, V.; Waschbu¨sch, R.; Carran, J.;
Savignac, P. Synthesis 1998, 271–274; (f) Sato, H.; Isono,
N.; Miyoshi, I.; Mori, M. Tetrahedron 1996, 52, 8143–
8158; (g) Kawase, T.; Darabi, H. R.; Uchimiya, R.; Oda,
M. Chem. Lett. 1995, 499–500.
Acknowledgements
Financial support for this work has been provided by
the University of Alberta, the Alberta Science,
Research, and Technology Authority, and NSERC. We
also gratefully acknowledge NSERC for a summer
undergraduate research scholarship to Ms. Chernick.
14. Eisler, S.; Tykwinski, R. R. J. Am. Chem. Soc. 2000, 122,
10736–10737.
References
15. For a related process, see: Tobe, Y.; Iwasa, N.; Umeda,
R.; Sonoda, M. Tetrahedron Lett. 2001, 42, 5485–5488.
16. For other methods of diyne synthesis, see: (a) Alami, M.;
Ferri, F. Tetrahedron Lett. 1996, 37, 2763–2766; (b)
1. Stiegman, A. E.; Graham, E.; Perry, K. J.; Khundkar, L.
R.; Cheng, L.-T.; Perry, J. W. J. Am. Chem. Soc. 1991,
113, 7658–7666.