1738
K. C. Majumdar et al. / Tetrahedron Letters 51 (2010) 1736–1738
Med. Chem. 1970, 13, 403; (b) Klayman, D. L.; Scovill, J. P.; Bartosevich, J. F.;
Table 2
Summarized results of the Heck reactiona
Mason, C. J. J. Med. Chem. 1979, 22, 1367; (c) Vedejs, E.; Galante, R. J.; Goekjian,
P. G. J. Am. Chem. Soc. 1998, 120, 3613; (d) Ma, D.; Tang, G.; Kozikowski, A. P.
Org. Lett. 2002, 4, 2377; (e) Stærk, D.; Witt, M.; Oketch-Rabah, H. A.;
Jaroszewski, J. W. Org. Lett. 2003, 5, 2793.
Entry Precursors
Time
(h)
Products
Yieldsc
(%)
4. (a) Illuminati, G.; Mandolini, L. Acc. Chem. Res. 1981, 14, 95; (b) Evans, P. A.;
Holmes, A. B. Tetrahedron 1991, 47, 9131; (c) Petasis, N. A.; Patane, M. A.
Tetrahedron 1992, 48, 5757; (d) Mehta, G.; Singh, V. Chem. Rev. 1999, 99, 881;
(e) Yet, L. Chem. Rev. 2000, 100, 2963; (f) Ma, S.; Gu, Z. J. Am. Chem. Soc. 2006,
128, 4942.
5. For a recent review, see: (a) Maier, M. E. Angew. Chem., Int. Ed. 2000, 39, 2073;
For selected examples, see: (b) Chattopadhyay, S. K.; Karmakar, S.; Biswas, T.;
Majumdar, K. C.; Rahaman, H.; Roy, B. Tetrahedron Rep. 2007, 63, 3919; (c)
Paquette, L. A.; Leit, S. M. J. Am. Chem. Soc. 1999, 121, 8126; (d) Cook, G. R.;
Shanker, P. S.; Peterson, S. L. Org. Lett. 1999, 1, 615; (e) Mori, M.; Kitamura, T.;
Sakakibara, N.; Sato, Y. Org. Lett. 2000, 2, 543.
6. For other recent synthesis of medium-ring heterocycles, see: (a) Majumdar, K.
C.; Rahaman, H.; Muhuri, S.; Roy, B. Synlett 2006, 466; (b) Majumdar, K. C.;
Islam, R.; Rahaman, H.; Roy, B. Org. Biomol. Chem. 2006, 4, 2393; (c) Majumdar,
K. C.; Muhuri, S.; Rahaman, H.; Islam, R.; Roy, B. Chem. Lett. 2006, 35, 1430; (d)
Majumdar, K. C.; Chattopadhyay, B.; Chakrovorty, S. Synthesis 2009, 674; (e)
Monovich, L. G.; Hue´rou, Y. L.; Rönn, M.; Molander, G. A. J. Am. Chem. Soc. 2000,
122, 52.
7. (a) Majumdar, K. C.; Cahttopadhyay, B.; Samanta, S. Tetrahedron Lett. 2009, 50,
3101; (b) Majumdar, K. C.; Samanta, S.; Chattopadhyay, B. Tetrahedron Lett.
2009, 50, 4866; (c) Majumdar, K. C.; De, R. N.; Chattopadhyay, B.; Roy, B. Synlett
2009, 2083; (d) Majumdar, K. C.; Ansary, I.; Sinha, B.; Chattopadhyay, B.
Synthesis 2009, 3593; (e) Majumdar, K. C.; Mondal, S.; De, N. Synlett 2008, 2851.
8. Mull, R. P.; Mizzoni, R. H.; Dapero, M. R.; Egbert, M. E. J. Org. Chem. 1962, 5, 944.
9. Paudler, W. W.; Zeiler, A. G. J. Org. Chem. 1969, 34, 2138.
Ts
Ts
N
N
O
O
Br
O
O
1a
6
6
90
88
N
N
4a
8a
O
O
O
N
N
O
O
O
O
N
N
O
Ts
Ts
N
N
Br
2a
N
N
8b
4b
Ts
Ts
N
N
3a
6
6
84
86
O
O
O
O
Br
N
N
9c
5c
Ts
Ts
N
O
N
10. See for example: (a) Nakayama, T.; Harada, N.; Asano, M.; Nomura, N.; Saito, T.;
Mishima, A.; Okajima, K. J. Pharmacol. Exp. Ther. 2007, 322, 582; (b) Culmsee, C.;
Gerling, N.; Landshamer, S.; Rickerts, B.; Duchstein, H. J.; Umezawa, K.;
Klumpp, S.; Krieglstein, J. J. Mol. Pharmacol. 2005, 68, 1006; (c) Mixcoatl-
Zecuatl, T.; Flores-Murrieta, F. J.; Granados-Soto, V. Eur. J. Pharmacol. 2006, 531,
87.
11. Yoshida, H.; Shirakawa, E.; Honda, Y.; Hiyama, T. Angew. Chem., Int. Ed. 2002,
41, 3247.
12. Klapars, A.; Parris, S.; Anderson, K. W.; Buchwald, S. L. J. Am. Chem. Soc. 2004,
126, 3529.
4a
Br
N
N
9d
5d
O
O
O
O
O
O
O
O
O
N
N
N
N
5a
6
85
NTs
NTs
N
10e
N
6e
Br
13. Koriatopoulou, K.; karousis, N.; Varvounis, G. Tetrahedron 2008, 64, 10009.
14. Potapov, V. V.; Fetisova, N. A.; Nikitin, A. V.; Ivachtchenko, A. V. Tetrahedron
Lett. 2009, 50, 2790.
O
O
N
15. BouzBouz, S.; Sanselme, M. Tetrahedron Lett. 2009, 50, 5884.
16. De Vries, A. H. M.; Mulders, J. M. C. A.; Mommers, J. H. M.; Henderickx, H. J. W.;
de Vries, J. G. Org. Lett. 2003, 5, 3285.
17. (a) Gazith, M.; Noys, R. M. J. Am. Chem. Soc. 1955, 77, 6091; (b) Gardner, I. J.;
Noys, R. M. J. Am. Chem. Soc. 1961, 83, 240.
NTs
NTs
NTs
N
6b
4
4
90
92
Br
7f
11f
18. General procedure for the preparation of the Heck-precursor 4a: A mixture of the
compound 2a (300 mg, 1.07 mmol), tosylated-2-bromoaniline 3a (421 mg,
1.29 mmol) and anhydrous K2CO3 (1.0 g) was refluxed in acetone (50 mL) for
4–6 h. in the presence of sodium iodide. The reaction mixture was cooled,
filtered and the solvent was removed. The crude product was purified by
column chromatography over silica gel (60–120 mesh) using petroleum ether–
ethyl acetate (3:2) as eluent to give 4a in 88% yield. Compound 4a: Yield: 88%,
O
O
N
N
NTs
7b
Br
7g
11g
solid; mp 190–192 °C; IR(KBr): m ;
max = 1648, 1676, 2925 cmÀ1 1H NMR (CDCl3,
500 MHz): dH = 7.73 (d, 1H, J = 7.7 Hz), 7.61 (d, 1H, J = 9.4 Hz), 7.54 (d, 2H,
J = 7.9 Hz), 7.49 (d, 1H, J = 7.7 Hz), 7.42 (d, 1H, J = 9.1 Hz), 7.28–7.33 (m, 3H),
7.17–7.20 (m, 3H), 6.77 (d, 1H, J = 9.4 Hz), 4.63 (br s, 1H), 4.36 (q, 2H,
J = 7.0 Hz), 3.89 (br s, 1H), 3.24 (s, 3H), 2.39 (s, 3H), 1.38 (t, 3H, J = 7.0 Hz) ppm.
13C NMR (CDCl3, 100 MHz): dC = 12.7, 21.5, 37.6, 37.9, 51.7, 115.8, 121.8, 123.2,
124.4, 127.2, 127.8, 128.0, 129.2, 129.3, 130.0, 133.3, 135.0, 136.3, 137.1, 137.7,
138.1, 138.6, 143.5, 161.6, 167.8 ppm. HRMS: m/z calcd for C27H26BrN3O4S:
[M++Na]: 590.0725, [M++Na+2]: 592.0708; found: 590.0725, 592.0725.
a
b
c
Catalyst used 10 mol % Pd(PPh3)4.
Catalyst used 10 mol % Pd(OAc)2.
Isolated yield of products.
Acknowledgements
19. General procedure for the synthesis of the compound 8a by Heck reaction: A
mixture of 4a (100 mg, 0.17 mmol), tetrabutylammonium bromide (85.2 mg,
0.26 mmol) and anhydrous potassium acetate (41.6 mg, 0.42 mmol) was taken
in N,N-dimethylformamide (DMF) (10 mL) under nitrogen atmosphere.
Pd(PPh3)4 (10 mol %, 20.3 mg) was added and the reaction mixture was
stirred at 120 °C for 6 h. The reaction mixture was cooled, water (20 mL) was
added and extracted with ethyl acetate (3 Â 30 mL). The ethyl acetate extract
was washed with water (2 Â 40 mL), followed by brine (30 mL). The organic
layer was dried (Na2SO4), and the solvent was evaporated to give a crude
product. This was purified by column chromatography over silica gel (230–400
mesh) using petroleum ether and ethyl acetate (3:2) as an eluent. The product
8a was isolated as a white solid in 90% yield. Similarly the other compounds
8b–11g were prepared in 84–92% yields. Compound 8a: Yield: 90%, solid; mp
We thank the DST (New Delhi) and CSIR (New Delhi) for finan-
cial assistance. Two of us (K.R. and S.G.) are grateful to the CSIR
(New Delhi) for their research fellowships.
References and notes
1. (a) Devon, T. K.; Scott, A. I.. In Handbook of Naturally Occurring Compounds;
Academic Press: New York and London, 1972; Vol. 2; (b) Faulkner, D. J. Nat.
Prod. Rep. 1984, 1. 251, 551; 1986, 3, 1; 1987, 4, 539; 1989, 5, 613; For a recent
review, see: (c) Evans, P. A.; Holmes, A. B. Tetrahedron 1991, 47, 9131.
2. For selected examples for seven-membered heterocycles, see: (a) Duong, T.;
Prager, R. H.; Tippett, J. M.; Ward, A. D.; Kerr, D. I. Aust. J. Chem. 1976, 29, 2667;
(b) Boros, C.; Hamilton, S. M.; Katz, B.; Kulanthaivel, P. J. Antibiot. 1994, 47,
1010; (c) Ishihara, Y.; Hirai, K.; Miyamoto, M.; Goto, G. J. Med. Chem. 1994, 37,
216–218 °C; IR(KBr):
m ;
max = 1656, 1680, 2925 cmÀ1 1H NMR (CDCl3,
400 MHz): dH = 7.98 (d, 1H, J = 7.6 Hz), 7.65–7.70 (m, 2H), 7.54 (d, 1H,
J = 9.2 Hz), 7.45 (t, 1H, J = 7.6 Hz), 7.31–7.35 (m, 3H), 7.23–7.28 (m, 3H), 6.74
(d, 1H, J = 9.2 Hz), 4.62 (s, 2H), 4.29 (q, 2H, J = 6.8 Hz), 3.23 (s, 3H), 2.51 (s, 3H),
1.37 (t, 3H, J = 6.8 Hz) ppm. 13C NMR (CDCl3, 100 MHz): dC = 12.7, 22.0, 37.5,
38.4, 49.1, 115.6, 119.7, 121.6, 123.0, 124.6, 124.8, 125.5, 125.7, 126.5, 128.7,
130.1, 132.1, 132.4, 136.1, 138.1, 138.2, 138.3, 142.7, 161.4, 166.6 ppm. HRMS:
m/z calcd for C27H25N3O4S; [M++H] 488.1638; found: 488.1641.
´
2292; (d) Morıs-Varas, F.; Qian, X.-H.; Wong, C.-H. J. Am. Chem. Soc. 1996, 33,
7647.
3. For selected examples for eight-membered heterocycles, see: (a) Basil, B.;
Coffee, E. C. J.; Gell, D. L.; Maxwell, D. R.; Sheffield, D. J.; Wooldridge, K. R. H. J.