LETTER
Synthesis of Pyranocoumarin Derivatives in Water
2851
(4) Duh, C.-Y.; Wang, S.-K.; Wu, Y.-C. Phytochemistry 1991,
30, 2812.
Table 2 Synthesis of Pyrano[3,2-c]coumarins 9
Entry Product R1
R2
Time (min) Yield (%)
(5) (a) Mali, R. S.; Joshi, P. P.; Sandhu, P. K.; Manekar-Tilve,
A. J. Chem. Soc., Perkin Trans. 1 2002, 371; and references
cited therein. (b) Xie, L.; Takeuchi, Y.; Cosentino, L. M.;
McPhail, A. T.; Lee, K. H. J. Med. Chem. 2001, 44, 664.
(c) Nicolaides, D. N.; Gautam, D. R.; Litinas, K. E.;
Hadjipavlou-Litina, D. J.; Fylaktakidou, K. C. Eur. J. Med.
Chem. 2004, 39, 323. (d) Melliou, E.; Magiatis, P.; Mitaku,
S.; Skaltsounis, A.-L.; Chinou, E.; Chinou, I. J. Nat. Prod.
2005, 68, 78. (e) Galinis, D. L.; Fuller, R. W.; McKee, T. C.;
Cardellina, J. H. II.; Gulakowski, R. J.; McMahon, J. B.;
Boyd, M. R. J. Med. Chem. 1996, 39, 507.
1
2
9a
9b
9c
9d
9e
9f
4-O2NC6H4
Ph
COOEt
COOEt
COOEt
COOEt
COOEt
COOEt
COOEt
COOEt
CN
15
15
20
20
15
20
20
15
22
20
15
20
20
25
25
15
88
90
80
83
86
82
80
85
80
82
85
90
85
80
79
92
3
4-MeOC6H4
4-MeC6H4
4-FC6H4
2-furyl
4
5
6
(6) Mali, R. S.; Pandhare, N. A.; Sindkhedkar, M. D.
Tetrahedron Lett. 1995, 36, 7109.
7
9g
9h
9i
2-thienyl
4-ClC6H4
4-ClC6H4
4-MeOC6H4
4-O2NC6H4
Ph
(7) For some selected examples, see: (a) Moreau, J.; Hubert, C.;
Batany, J.; Toupet, L.; Roisnel, T.; Hurvois, J.-P.; Renaud,
J.-L. J. Org. Chem. 2009, 74, 8963. (b) Appendino, G.;
Cravotto, G.; Giovenzana, G. B.; Palmisano, G. J. Nat. Prod.
1999, 62, 627. (c) Nair, V.; Vinod, A. U.; Ramesh, R.;
Menon, R. S.; Varma, L.; Mathews, S.; Chiaroni, A.
Heterocycles 2002, 58, 147. (d) Page, P. C. B.; Appleby,
L. F.; Day, D.; Chan, Y.; Buckley, B. R.; Allin, S. M.;
McKenzie, M. J. Org. Lett. 2009, 11, 1991. (e) Shen, Y.-C.;
Wang, L.-T.; Chen, C.-Y. Tetrahedron Lett. 2004, 45, 187.
(f) Litinas, K. E.; Symeonidis, T. S. Tetrahedron 2010, 66,
1289.
(8) (a) Yadav, J. S.; Subba Reddy, B. V.; Shubashree, S.;
Sadashiv, K.; Krishna Rao, D. J. Mol. Catal. A: Chem. 2007,
272, 128. (b) Heravi, M. M.; Baghernejad, B.; Oskooie,
H. A.; Hekmatshoar, R. Tetrahedron Lett. 2008, 49, 6101.
(c) Alizadeh, A.; Rostomnia, S.; Esmaili, A. A. Synthesis
2007, 709. (d) Vasuki, G.; Kumaravel, K. Tetrahedron Lett.
2008, 49, 5636.
(9) (a) De Silva, R. A.; Santra, S.; Andreana, P. R. Org. Lett.
2008, 10, 4541. (b) Shaabani, A.; Ali Rezayan, H.;
Ghasemi, S.; Sarvary, A. Tetrahedron Lett. 2009, 50, 1456.
(c) Heravi, M. M.; Baghernejad, B.; Oskooie, H. A.
Tetrahedron Lett. 2009, 50, 767. (d)Fujiwara, S.;Asanuma,
Y.; Shin-ike, T.; Kambe, N. J. Org. Chem. 2007, 72, 8087.
(10) For selected reviews, see: (a) Koldobskii, G. I.; Ostrovskii,
V. A. Chem. Heterocycl. Compd. 1983, 19, 1141. (b) Shen,
Z.-X.; Kong, A.-D.; Chen, W.-X.; Zhang, Y.-W. Chin. J.
Org. Chem. 2003, 23, 10. (c) Ooi, T.; Maruoka, K. Angew.
Chem. Int. Ed. 2007, 46, 4222.
(11) (a) Sarma, R.; Prajapati, D. Synlett 2008, 3001.
(b) Prajapati, D.; Gohain, M.; Thakur, A. J. Bioorg. Med.
Chem. Lett. 2006, 16, 3537. (c) Prajapati, D.; Thakur, A. J.
Tetrahedron Lett. 2005, 46, 1433. (d) Gohain, M.;Prajapati,
D.; Gogoi, B. J.; Sandhu, J. S. Synlett 2004, 1179.
(12) CCDC-784897 contains the supplementary crystallographic
data for compound 10a. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre
8
9
10
11
12
13
14
15
16
9j
CN
9k
9l
CN
CN
9m
9n
9o
9p
4-MeC6H4
2-furyl
CN
CN
2-thiophenyl CN
4-FC6H4 CN
the presence of a phase-transfer catalyst.13 The use of wa-
ter as the reaction medium makes the process economical
and environmentally friendly. The methodology offers
further advantages such as short reaction time, mild reac-
tion conditions, operational simplicity and an easy work-
up procedure, which makes it an attractive strategy for the
synthesis of pyranocoumarin derivatives.
Acknowledgment
We thank DST, New Delhi for financial support. One of us (R.S.)
thanks the Council of Scientific and Industrial Research, New Delhi
(India), for the award of a research fellowship. Dr R. K. Boruah,
Scientist of the Analytical Chemistry Division, NEIST, Jorhat is
gratefully acknowledged for single crystal analysis. We also thank
the Director, NEIST, Jorhat for his keen interest and constant en-
couragement.
References and Notes
(13) (a) Typical procedure for the synthesis of 4a–l:
A mixture of alkyl isocyanide (1 mmol), dialkyl acetylene-
dicarboxylate (1 mmol) and 1,3-dicarbonyl compound
(1 mmol) in H2O (5 mL), in the presence of TBAB (10
mol%) was stirred at 80 °C until the reaction was complete
as indicated by TLC. The crude solid product was filtered,
washed with H2O, dried and purified by column
(1) (a) McKee, T. C.; Covington, C. D.; Fuller, R. W.; Bokesch,
H. R.; Young, S.; Cardellina, J. H. II.; Kadushin, M. R.;
Soejarto, D. D.; Stevens, P. F.; Cragg, G. M.; Boyd, M. R.
J. Nat. Prod. 1998, 61, 252. (b) Melliou, E.; Magiatis, P.;
Mitaku, S.; Skaltsounis, A.-L.; Chinou, E.; Chinou, I. J. Nat.
Prod. 2005, 68, 8. (c) Kostova, I. Curr. Med. Chem. 2005, 5,
29. (d) Basile, A.; Sorbo, S.; Spadaro, V.; Bruno, M.;
Maggio, A.; Faraone, N.; Rosselli, S. Molecules 2009, 14,
939.
(2) Ju, Y.; Still, C. C.; Sacalis, J. N.; Li, J.; Ho, C. T. Phytother.
Res. 2001, 15, 441.
(3) Kapoor, S. K.; Kohli, J. M.; Sharma, Y. N.; Zaman, A.
Phytochemistry 1972, 11, 477.
chromatography (EtOAc–hexane, 3:7). The products thus
obtained were characterized by their IR, NMR spectroscopic
and mass spectrometric data. Dimethyl 2-(cyclohexyl-
amino)-5-oxo-4H,5H-pyrano[3,2-c]chromene-3,4-
dicarboxylate (4a): White solid; mp 198–200 °C; IR
(CHCl3): 3264.9 (N–H), 1732.6, 1686.3, 1659.4 (C=O) cm–1.
Synlett 2010, No. 19, 2847–2852 © Thieme Stuttgart · New York