J. Wang et al. / Tetrahedron Letters 50 (2009) 4978–4982
4981
Ph
Ph
.
Ph Ph
OH
FeCl3 6H2O
Ph
Ph
Ph
Ph
Ph
1a
3a
4a
2a
Ph
Ph
Ph
Ph
5a
Ph
6a
Scheme 1.
References and notes
Ph
.
1. (a) Harrowven, D. C.; Newman, N. A.; Knight, C. A. Tetrahedron Lett. 1998, 39,
6757; (b) Karaguni, I. M.; Glusenkamp, K. H.; Langerak, A.; Geisen, C.;
Ullrich, V.; Winde, G.; Moroy, T.; Muller, O. Bioorg. Med. Chem. Lett. 2002, 12,
709; (c) Kolanos, R.; Siripurapu, U.; Pullagurla, M.; Riaz, M.; Setola, V.; Roth,
B. L.; Dukat, M.; Glennon, R. A. Bioorg. Med. Chem. Lett. 2005, 15, 1987; (d)
Wang, Y.; Mo, S. Y.; Wang, S. J.; Li, S.; Yang, Y. C.; Shi, J. G. Org. Lett. 2005, 7,
1675.
FeCl3 6H2O (5 mol%)
Ph
Ph
HO
toluene, 40 o
C
Ph
1q
Ph
: 93 %
2q
2. Barberá, J.; Rakitin, O. A.; Ros, M. B.; Torroba, T. Angew. Chem., Int. Ed. 1998, 37,
296.
Scheme 2.
3. (a) Zargarian, D. Coord. Chem. Rev. 2002, 233–234, 157; (b) Alt, H. G.; Köppl, A.
Chem. Rev. 2000, 100, 1205; (c) Wang, B. Q. Coord. Chem. Rev. 2006, 250, 242.
4. Halterman, R. L. Chem. Rev. 1992, 92, 965.
5. (a) Kuninobu, Y.; Nishina, Y.; Shouho, M.; Takai, K. Angew. Chem., Int. Ed. 2006,
45, 2766; (b) Kuninobu, Y.; Kawata, A.; Takai, K. J. Am. Chem. Soc. 2005, 127,
13498; (c) Kuninobu, Y.; Tokunaga, Y.; Kawata, A.; Takai, K. J. Am. Chem. Soc.
2006, 128, 202.
6. (a) Duan, X. H.; Guo, L. N.; Bi, H. P.; Liu, X. Y.; Liang, Y. M. Org. Lett. 2006, 8,
3053; (b) Guo, L. N.; Duan, X. H.; Bi, H. P.; Liu, X. Y.; Liang, Y. M. J. Org. Chem.
2006, 71, 3325; (c) Zhang, D. H.; Liu, Z. J.; Yum, E. K.; Larock, R. C. J. Org. Chem.
2007, 72, 251; (d) Guan, Z. H.; Ren, Z. H.; Zhao, L. B.; Liang, Y. M. Org. Biomol.
Chem. 2008, 6, 1040.
at the 3-position. For example, treatment of 1m with 5 mol % FeCl3
gave only 2m (Table 2, entry 13), while 1n formed a 2:1 mixture of
2n and 2n0 under the same conditions (Table 2, entry 14). These
results indicate that the selectivity would favor the allylic cation
which is most stabilized to effect electrophilic attack unless the
nucleophilic benzene ring has a strong electron-deficient substitu-
ent (such as nitro). In addition, it was found that the introduction
of either the electron-donating or weak electron-withdrawing
(e.g., chloro) group at the para-position of the nucleophilic ben-
zene ring had only a slight influence on the reactivity compared
with those without a substituent on the aromatic ring (Table 2,
entries 10 and 11). An alcohol 1o could also be applied in this
reaction to form compound 2o in 56% yield (Table 2, entry 15).
The results described above clearly demonstrate that, in the pres-
ent catalytic system, the different types and numbers of substitu-
ents on the indene skeleton could be controlled by applying allylic
alcohols bearing the desired types and numbers of substituents.
The allylic alcohol without a hydrogen at carbon–carbon double
bond positions (1q) used as a substrate also gave the cyclization
product in high yield (Scheme 2).
7. (a) Rayabarapu, D. K.; Cheng, C. H. Chem. Commun. 2002, 942; (b) Chang, K. J.;
Rayabarapu, D. K.; Cheng, C. H. J. Org. Chem. 2004, 69, 4781.
8. Dubé, P.; Toste, F. D. J. Am. Chem. Soc. 2006, 128, 12062.
9. (a) Skattebøl, L.; Boulette, B. J. Org. Chem. 1966, 31, 81; (b) Padwa, A.; Blacklock,
T. J.; Loza, R. J. Org. Chem. 1982, 47, 3712; (c) Lu, J. M.; Shi, M. Org. Lett. 2006, 8,
5317; (d) Yadav, V. K.; Kumar, N. V.; Parvez, M. Chem. Commun. 2007, 2281; (e)
Zhu, Z. B.; Shi, M. Chem. Eur. J. 2008, 14, 10219; (f) Hu, B.; Xing, S. Y.; Wang, Z.
W. Org. Lett. 2008, 10, 5481.
10. (a) Parham, W. E.; Egberg, D. C. J. Org. Chem. 1972, 37, 1545; (b) Lomberget, T.;
Bentz, E.; Bouyssi, D.; Balme, G. Org. Lett. 2003, 5, 2055; (c) Sun, X.; Izumk, K. J.;
Hu, C. Q.; Lin, G. Q. Chin. J. Chem. 2006, 24, 430; (d) Basavaiah, D.; Reddy, K. R.
Org. Lett. 2007, 9, 57.
11. (a) Yasuda, M.; Somyo, T.; Baba, A. Angew. Chem., Int. Ed. 2006, 45, 793; (b)
Rueping, M.; Nachtsheim, B. J.; Kuenkel, A. Org. Lett. 2007, 9, 825; (c)
Krishna, P. R.; Sekhar, E. R.; Prapurna, Y. L. Tetrahedron Lett. 2007, 48, 9048;
(d) Jana, U.; Biswas, S.; Maiti, S. Tetrahedron Lett. 2007, 48, 4065; (e) Jana,
U.; Maiti, S.; Biswas, S. Tetrahedron Lett. 2008, 49, 858; (f) Wu, W.; Rao, W.;
Er, Y. Q.; Loh, J. K.; Poh, C. Y.; Chan, P. W. H. Tetrahedron Lett. 2008, 49,
2620.
12. (a) Deno, N. C.; Pittman, C. U., Jr.; Turner, J. O. J. Am. Chem. Soc. 1965, 87, 2153;
(b) Pittman, C. U., Jr.; Miller, W. G. J. Am. Chem. Soc. 1973, 95, 2947; (c) Miller,
W. G.; Pittman, C. U., Jr. J. Org. Chem. 1974, 39, 1955; (d) Olah, G. A.; Asensio, G.;
Mayr, H. J. Org. Chem. 1978, 43, 1518; (e) Singh, G.; Ila, H.; Junjappa, H. Synthesis
1986, 744; (f) Gassman, P. G.; Ray, J. A.; Wenthold, P. G.; Mickelson, J. W. J. Org.
Chem. 1991, 56, 5143; (g) Jeong, I. H.; Park, Y. S.; Kim, M. S.; Song, Y. S. J. Fluorine
Chem. 2003, 120, 195; (h) Xi, Z.; Guo, R.; Mito, S.; Yan, H.; Kanno, K.; Nakajima,
K.; Takahashi, T. J. Org. Chem. 2003, 68, 1252; (i) Zhou, X. B.; Zhang, H. M.; Xie,
X.; Li, Y. Z. J. Org. Chem. 2008, 73, 3958; (j) Guo, S. H.; Liu, Y. H. Org. Biomol.
Chem. 2008, 6, 2064.
In summary, an experimentally convenient, efficient, and cheap
catalytic process for the synthesis of substituted indenes from aryl-
substituted allylic alcohols via an intramolecular Friedel–Crafts
reaction has been established. Significant substrate flexibility and
excellent control of the double bonds and substituent position ren-
der this an attractive method for the synthesis of versatile substi-
tuted indenes.
Acknowledgments
13. (a) Huang, W.; Wang, J. L.; Shen, Q. S.; Zhou, X. G. Tetrahedron Lett. 2007, 48,
3969; (b) Huang, W.; Wang, J. L.; Shen, Q. S.; Zhou, X. G. Tetrahedron 2007, 63,
11636; (c) Huang, W.; Shen, Q. S.; Wang, J. L.; Zhou, X. G. J. Org. Chem. 2008, 73,
1586; (d) Huang, W.; Zheng, P. Z.; Zhang, Z. X.; Liu, R. T.; Chen, Z. X.; Zhou, X. G.
J. Org. Chem. 2008, 73, 6845; (e) Wang, J. L.; Huang, W.; Zhang, Z. X.; Xiang, X.;
Liu, R. T.; Zhou, X. G. J. Org. Chem. 2009, 74, 3299.
We thank the NNSF of China, 973 program (2009CB825300),
NSF of Shanghai, and Shanghai Leading Academic Discipline Project
for financial support (B108).
14. (a) Bolm, C.; Legros, J.; Paih, J. L.; Zani, L. Chem. Rev. 2004, 104, 6217; (b)
Enthaler, S.; Junge, K.; Beller, M. Angew. Chem., Int. Ed. 2008, 47, 3317.
Supplementary data
procedure: To allylic alcohol 1 (0.5 mmol) in toluene (1 mL) was added
15. General
FeCl3ꢀ6H2O (6.7 mg, 0.025 mmol) under an argon atmosphere and then the
reaction mixture was stirred at 40 °C for 1 h. After completion of the reaction,
the mixture was quenched with water and extracted with ethyl acetate
(3 ꢁ 10 mL). The organic layers were combined and dried over Na2SO4. After
Supplementary data associated with this article can be found, in