ORGANIC
LETTERS
2007
Vol. 9, No. 11
2219-2222
FeCl3-Catalyzed Alkenylation of Simple
Arenes with Aryl-Substituted Alkynes
Ruoshi Li, Sunewang R. Wang, and Wenjun Lu*
Department of Chemistry, Shanghai Jiao Tong UniVersity, 800 Dongchuan Road,
Shanghai 200240, China
Received March 26, 2007
ABSTRACT
An addition of electron-rich arenes to aryl-substituted alkynes to form 1,1-diaryl alkenes is carried out in the presence of FeCl3 as catalyst
under mild conditions.
Functionalization of simple arenes plays an important role
in the synthesis of pharmaceuticals, agrochemicals, and fine
chemicals. A well-known process involving the formation
of new C-C bonds from aromatic C-H bonds is the
Friedel-Crafts alkylation of various arenes, especially
electron-rich arenes with alkyl halides, alcohols, or alkenes.1
On the other hand, the pioneering work on alkenylation of
simple arenes was an oxidative coupling of arenes with
alkenes in the presence of palladium complexes and a
rhodium-catalyzed addition of aromatic and heteroaromatic
compounds to alkynes in the presence of carbon monoxide.2
Thereafter, a few efficient methods of hydroarylation of
alkynes have been developed. In these processes, transition
metals as catalysts including rhodium,3 ruthenium,4 pal-
ladium,5 platinum,5 gold,6 or rare-metals7 are normally used,
and in some systems acids or ionic liquids are necessary.5a,b,7b
However, since these catalysts are expensive or the turnover
numbers of these processes are not very high, their large-
scale applications are restricted.
According to our knowledge, there is no example of the
alkenylation of arenes with alkynes using inexpensive
catalysts through an economical and efficient method.8
However, iron as an abundant, economical, and environ-
mentally friendly metal shows increasing and promising
catalytic abilities in many organic syntheses.9 In one
prominent case, iron has been proven to be a practical
alternative catalyst in an arylation of benzyl alcohols and
carboxylates, formerly catalyzed by expensive late transition
metals.9b Herein, we report a convenient FeCl3-catalyzed
(5) (a) Jia, C.; Piao, D.; Oyamada, J.; Lu, W.; Kitamura, T.; Fujiwara,
Y. Science 2000, 287, 1992. (b) Jia, C.; Lu, W.; Oyamada, J.; Kitamura,
T.; Matsuda, K.; Irie, M.; Fujiwara, Y. J. Am. Chem. Soc. 2000, 122, 7252.
(c) Lu, W.; Jia, C.; Kitamura, T.; Fujiwara, Y. Org. Lett. 2000, 2, 2927.
(6) (a) Reetz, M. T.; Sommer, K. Eur. J. Org. Chem. 2003, 3485. (b)
Shi, Z.; He, C. J. Org. Chem. 2004, 69, 3669. (c) Ne-vado, C.; Echavarren,
A. M. Chem. Eur. J. 2005, 11, 3155.
(7) (a) Tsuchimoto, T.; Maeda, T.; Shirakawa, E.; Kawakami, Y. Chem.
Commun. 2000, 1573. (b) Song, C.; Jung, D.; Choung, S.; Roh, E.; Lee, S.
Angew. Chem. 2004, 116, 6309; Angew. Chem., Int. Ed. 2004, 43, 6183.
(8) Ni(0)-catalyzed alkenylation of heteroarenes. See: Nakao, Y.;
Kanyiva, K.; Oda, S.; Hiyama, T. J. Am. Chem. Soc. 2006, 128, 8146.
(9) (a) Bolm, C.; Legros, J.; Paih, J.; Zani, L. Chem. ReV. 2004, 104,
6217. (b) Jovel, I.; Mertins, K.; Kischel, J.; Zapf, A.; Beller, M. Angew.
Chem. 2005, 117, 3981; Angew. Chem., Int. Ed. 2005, 44, 3913. (c) Kischel,
J.; Jovel, I.; Mertins, K.; Zapf, A.; Beller, M. Org. Lett. 2006, 8, 19. (d)
Nakamura, M.; Hirai, A.; Nakamura, E. J. Am. Chem. Soc. 2000, 122, 978.
(e) Komeyama, K.; Morimoto, T.; Takaki, K. Angew. Chem. 2006, 118,
3004; Angew. Chem., Int. Ed. 2006, 45, 2938.
(1) (a) Olah, G. A.; Krishnamurit, R.; Prakash, G. K. S. Friedel-Crafts
Alkylations in ComprehensiVe Organic Synthesis; Trost, B. M., Fleming,
I., Eds.; Pergamon: Oxford, UK, 1991. (b) Carey, F.; Sundberg, R. AdVance
Organic Chemistry, 4th ed.; Kluwer Academic/Plenum Publishers: New
York, 2000; Part B.
(2) (a) Moritani, I.; Fujiwara, Y. Tetrahedron Lett. 1967, 1119. (b) Jia,
C.; Kitamura, T.; Fujiawara, Y. Acc. Chem. Res. 2001, 34, 633. (c) Hong,
P.; Cho, B.-R.; Yamazaki, H. Chem. Lett. 1979, 339. (d) Hong, P.; Cho,
B.-R.; Yamazaki, H. Chem. Lett. 1980, 507.
(3) (a) Ritleng, V.; Sirlin, C.; Pfeffer, M. Chem. ReV. 2002, 102, 1731.
(b) Boese, W. T.; Goldman, A. S. Organometallics 1991, 10, 782.
(4) (a) Murai, S.; Kakiuchi, F.; Sekine, S.; Tanaka, Y.; Kamatani, A.;
Sonoda, M.; Chatani, N. Nature 1993, 366, 529. (b) Merlic, C. A.; Pauly,
M. E. J. Am. Chem. Soc. 1996, 118, 11319. (c) Murakami, M.; Hori, S. J.
Am. Chem. Soc. 2003, 125, 4720.
10.1021/ol070737u CCC: $37.00
© 2007 American Chemical Society
Published on Web 05/03/2007