Chemistry of Materials
ARTICLE
renders diarylation a significant reaction product. This is dis-
advantageous for the formal synthesis of 3, 8, and 9 in which only
one arylation is desired. Five equivalents of thiophene coupling
partner are required to avoid diarylation and gives 13 and 20 in
Aldrichim. Acta 2007, 40, 35. (c) Li, B.-J.; Yang, S.-D.; Shi, Z.-J. Synlett
2008, 949. (d) McGlacken, G. P.; Bateman, L. M. Chem. Soc. Rev. 2009,
3
8, 2447. (e) Ackermann, L.; Vicente, R.; Kapdi, A. R. Angew. Chem., Int.
Ed. 2009, 48, 9792.
5) For direct arylation of thiophenes see: (a) Ohta, A.; Akita, Y.;
(
5
2% and 86% yield respectively. Also, six equivalents are required
to isolate 19 in 66% yield. Again, the use of excess thiophene is
Ohkama, T.; Chiba, M.; Fukunaga, R.; Miyafuji, A.; Nakata, T.; Tani, N.;
Aoyagi, Y. Heterocycles 1990, 31, 1951. (b) Gozzi, C.; Lavenot, L.; Ilg, K.;
Penalva, V.; Lemaire, M. Tetrahedron Lett. 1997, 38, 8867. (c) Pivsa-Art,
S.; Satoh, T.; Kawamura, Y.; Miura, M.; Nomura, M. Bull. Chem. Soc. Jpn.
25
mitigated because it is inexpensive, easily handled and less toxic
compared to organometallic coupling partners. However, one
potential solution to this problem would be to employ a chlorine
1
998, 71, 467. (d) Lavenot, L.; Gozzi, C.; Ilg, K.; Penalva, V.; Lemaire,
5t
atom as an activating/blocking group. Conversly, if diarylation
M. J. Organomet. Chem. 1998, 567, 49. (e) Okazawa, T.; Satoh, T.;
Miura, M.; Nomura, M. J. Am. Chem. Soc. 2002, 124, 5286. (f) Glover, B.;
Harvey, K. A.; Liu, B.; Sharp, M. J.; Tymoschenko, M. F. Org. Lett. 2003,
is desired such as with 6 this reactivity can also be advantageous.
0
The ideal mol ratio of 2:1 aryl bromide to 2,2 -bithiophene can be
5
2
, 301. (g) Yokooji, A.; Satoh, T.; Miura, M.; Nomura, M. Tetrahedron
004, 60, 6757. (h) Fournier dit Chabert, J.; Joucla, L.; David, E.;
employed and gives 6 in 87% yield.
Lemaire, M. Tetrahedron 2004, 60, 3221. (i) David, E.; Perrin, J.; Pellet-
Rostaing, S.; Fournier dit Chabert, J.; Lemaire, M. J. Org. Chem. 2005,
70, 3569. (j) Kobayashi, K.; Sugie, A.; Takahashi, M.; Masui, K.; Mori, A.
Org. Lett. 2005, 7, 5083. (k) Chiong, H. A.; Daugulis, O. Org. Lett. 2007,
’
CONCLUSION
In conlusion, we have demonstrated the viabilty of direct
arylation for the (formal) synthesis of a broad range of thiophene
based organic electronic materials. Direct arylation has several
advantages to traditional cross-coupling methods currently used
for the construction organic electronic materials and should be
added to the “synthetic toolbox” of organic materials chemists.
Direct arylation should be useful for the rapid and atom
economical synthesis of an ever growing quantity of organic
electronic materials as well as streamline the synthesis of new
thiophene-based organic electronic materials.
9
, 1449. (l) Battace, A.; Lemhadri, M.; Zair, T.; Doucet, H.; Santelli, M.
Adv. Synth. Catal. 2007, 349, 2507. (m) Yanagisawa, S.; Sudo, T.;
Noyori, R.; Itami, K. J. Am. Chem. Soc. 2006, 128, 11748. (n) Arai, N.;
Miyaoku, T.; Teruya, S.; Mori, A. Tetrahedron Lett. 2008, 49, 1000. (o)
Nakano, M.; Tsurugi, H.; Satoh, T.; Miura, M. Org. Lett. 2008, 10, 1851.
(
(
p) Po ꢀz gan, F.; Roger, J.; Doucet, H. ChemSusChem 2008, 1, 404–407.
q) Roger, J.; Doucet, H. Org. Biomol. Chem. 2008, 6, 169. (r) Li ꢁe gault,
B.; Lapointe, D.; Caron, L.; Vlassova, A.; Fagnou, K. J. Org. Chem. 2009,
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(
t) Li ꢁe gault, B.; Petrov, I.; Gorelsky, S. I.; Fagnou, K. J. Org. Chem. 2010,
5, 1047. (u) Ren ꢁe , O.; Fagnou, K. Org. Lett. 2010, 12, 2116. (v) Ueda,
K.; Yanagisawa, S.; Yamaguchi, J.; Itami, K. Angew. Chem., Int. Ed. 2010,
9, 8946.(w) Chen, L.; Roger, J.; Bruneau, C.; Dixneuf, P. H.; Doucet, H.
Chem. Commun. 2011, Advance Article, DOI: 10.1039/c0cc04302h.
6) (a) Wang, Q.; Takita, R.; Kikuzaki, Y.; Ozawa, F. J. Am. Chem.
7
’
ASSOCIATED CONTENT
4
S
Supporting Information. Copies of NMR spectra for all
b
coupling products. This material is available free of charge via the
Internet at http://pubs.acs.org
(
Soc. 2010, 132, 11420. (b) Masui, K.; Mori, A.; Takamura, K.; Okano, K.;
Kinoshita, M.; Ikeda, T. Org. Lett. 2004, 6, 2011.
(7) Lafrance, M.; Fagnou, K. J. Am. Chem. Soc. 2006, 128, 16496.
’
AUTHOR INFORMATION
(
8) Lafrance, M.; Lapointe, D.; Fagnou, K. Tetrahedron 2008,
4, 6015.
9) Perepichka, I. F.; Perepichka, D. F.; Handbook of Thiophene-
Based Materials; John Wiley & Sons: Chichester, U.K., 2009.
10) Gorelsky, S. I.; Lapointe, D.; Fagnou, K. J. Am. Chem. Soc. 2008,
30, 10848.
11) Vogtle, M. M.; Beck, D. A. S.; Leutert, T.; Ossola, F.; La
Vecchia, L. ARKIVOC 2008, 210.
12) Cremer, J.; Bauerle, P. J. Mater. Chem. 2006, 16, 874.
Corresponding Author
6
*E-mail: dschi064@uottawa.ca.
(
Notes
Prof. Keith Fagnou passed away on November 11, 2009.
(
†
1
(
’
ACKNOWLEDGMENT
(
We thank NSERC, the University of Ottawa, Amgen, Eli Lilly,
and AstraZeneca for supporting this work. DJS thanks NSERC
for a postgraduate scholarship (PGS-D).
(13) (a) Park, S. W.; Son, K.-I.; Ko, M. J.; Kim, K.; Park, N.-G. Synth.
Met. 2009, 159, 2571. (b) Lee, K.; Park, S. W.; Ko, M. J.; Kim, K.; Park,
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(14) (a) Roquet, S.; Cravino, A.; Leriche, P.; Aleveque, O.; Frere, P.;
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dx.doi.org/10.1021/cm103483q |Chem. Mater. 2011, 23, 1594–1600