6226
A. Kumar et al. / Tetrahedron Letters 51 (2010) 6224–6226
4. Ben-Alloum, A.; Bakkas, S.; Soufiaoui, M. Tetrahedron Lett. 1997, 38, 6395.
Table 3
Biocatalytic synthesis of benzoxazolesa
5. Roe, A.; Tucker, W. P. J. Heterocycl. Chem. 1965, 2, 148.
6. (a) Hutchinson, I.; Stevens, M. F. G.; Westwell, A. D. Tetrahedron Lett. 2000, 41,
425; (b) Spitulnik, M. J. Synthesis 1976, 730.
Entry
R
Product
Time (h)
Yield (%)
7. Ranu, B. C.; Jana, R.; Dey, S. Chem. Lett. 2004, 33, 274.
8. Li, Y.; Wang, Y. L.; Wang, J. Y. Chem. Lett. 2006, 35, 460.
1
2
3
4
5
C6H5
4a
4b
4c
4d
4e
12
12
12
12
12
91
94
98
98
89
4-CH3OC6H4
4-CH3C6H4
4-(CH3)2NC6H4
4-ClC6H4
9. Moghadhan, F. M.; Ismaili, H.; Bardajee, G. R. Heteroat. Chem. 2006, 17, 136.
10. Ryabukhin, S. V.; Plaskon, A. S.; Volochnyuk, D. M.; Tolmachev, A. A. Synthesis
2006, 3715.
11. Praveen, C.; Hemanthkumar, K.; Muralidharan, D.; Perumal, P. T. Tetrahedron
2008, 64, 2369.
12. Bahrami, K.; Khodaei, M. M.; Nali, F. J. Org. Chem. 2008, 73, 6835.
13. Bose, S. D.; Idrees, M.; Srikanth, B. Synthesis 2007, 819.
14. (a) Kumar, A.; Maurya, R. A. Tetrahedron 2008, 64, 3471–3482; (b) Kumar, A.;
Maurya, R. A. Tetrahedron Lett. 2008, 49, 5471–5474; (c) Kumar, A.; Maurya, R.
A. Tetrahedron 2007, 63, 1946–1952; (d) Kumar, A.; Maurya, R. A.; Sharma, S.
Bioorg. Med. Chem. 2009, 19, 4432; (e) Kumar, A.; Sharma, S.; Maurya, R. A.
Tetrahedron Lett. 2009, 43, 5937–5940; (f) Kumar, A.; Kumar, M.; Gupta, M. K.
Tetrahedron Lett. 2009, 50, 7024–7027; (g) Kumar, A.; Gupta, M. K.; Kumar, M.
Tetrahedron Lett. 2010, 51, 1582–1584; (h) Kumar, A.; Maurya, R. A. Tetrahedron
Lett. 2007, 48, 3887–3890; (i) Kumar, A.; Maurya, R. A. Tetrahedron Lett. 2007,
48, 4569–4571.
a
Citrate buffer (pH 6.0) was used as a solvent.
H
N
N
GOX/CPO
d-Glucose
S
S
citrate buffer pH= 6.0
3a
5
Yield= 91%
15. (a) Hager, L. P.; Lakner, F. J.; Basavapathruni, A. J. Mol. Catal. B: Enzym. 1998, 5,
95–101; (b) Van Deurzen, M. P. J.; van Rantwijk, F.; Sheldon, R. A. Tetrahedron
1997, 13183–13220.
Scheme 2. Synthesis of 3a from 2-phenyl-2,3-dihydrobenzo[d]thiazoles.
16. (a) Allain, E. J.; Hager, L. P.; Deng, J.; Jacobsen, E. N. J. Am. Chem. Soc. 1993, 115,
4415–4416; (b) Dexter, A. F.; Lakner, F. J.; Campbell, R. A.; Hager, L. P. J. Am.
Chem. Soc. 1995, 117, 6412–6413.
17. (a) Hu, S.; Hager, J. P. J. Am. Chem. Soc. 1999, 121, 872–873; (b) Miller, V. P.;
Tschirret-Guth, R. A.; Ortiz de Montellano, P. R. Arch. Biochem. Biophys. 1995,
319, 333–340; (c) Zaks, A.; Dods, D. R. J. Am. Chem. Soc. 1995, 117, 10419–
10424.
In conclusion we have developed a highly efficient and environ-
ment friendly protocol for the synthesis of 2-substituted benzo-
thia/(oxa)zoles. We believe that our methodology may also be
applicable for the synthesis of a wide range of heterocycles.
18. (a) Colonna, S.; Gaggero, N.; Casella, L.; Carrea, G.; Pasta, P. Tetrahedron:
Asymmetry 1992, 3, 95–106; (b) Pezzotti, F.; Okrasa, K.; Therisod, M.
Tetrahedron: Asymmetry 2005, 16, 2618; (c) Okrasa, K.; Guibe´-Jampel, E.;
Therisod, M. J. Chem. Soc., Perkin Trans. 1 2000, 1077–1079; (d) Okrasa, K.;
Falcimaigne, A.; Guibe´-Jampel, E.; Therisod, M. Tetrahedron: Asymmetry 2002,
13, 519–522.
19. Corbett, M. D.; Chipko, B. R. Biochem. J. 1979, 183, 269–276.
20. Van Deurzen, M. P. J.; Seelbach, K.; van Rantwijk, F.; Kragl, U.; Sheldon, R. A.
Biocatal. Biotrans. 1997, 15, 1–16.
21. (a) Pezzotti, F.; Okrasa, K.; Therisod, M. Tetrahedron: Asymmetry 2005, 16,
2681–2683; (b) Okrasa, K.; Guibe-Jampel, E.; Therisod, M. J. Chem. Soc., Perkin
Trans. 1 2000, 1077–1079; (c) Okrasa, K.; Falcimaigne, A.; Guibe-Jampel, E.;
Therisod, M. Tetrahedron: Asymmetry 2002, 13, 519–522.
Acknowledgments
S.S. and R.A.M. are thankful to CSIR, New Delhi, for financial
support. The authors also acknowledge SAIF-CDRI for providing
spectral and analytical data.
References and notes
1. (a) Nagel, A. A.; Liston, D. R.; Jung, S.; Maher, M.; Vincent, L. A.; Chapin, D.;
Chen, Y. L.; Hubbard, S.; Ives, J. L.; Jones, S. B. J. Med. Chem. 1995, 38, 1084; (b)
Deluca, M. R.; Kerwin, S. M. Tetrahedron Lett. 1997, 38, 199; (c) Temiz, O.; Oren,
I.; Sener, E.; Yalcin, I.; Ucarturk, N. Farmaco 1998, 53, 337; (d) Sato, S.; Kajiura,
T.; Noguchi, M.; Takehana, K.; Kobayashi, T.; Tsuji, T. J. Antibiot. 2001, 54, 102;
(e) Sondhi, S. M.; Singh, N.; Kumar, A.; Lozach, O.; Meijer, L. Bioorg. Med. Chem.
2006, 14, 3758–3765; (f) Vinsova, J.; Cermakova, K.; Tomeckova, A.; Ceckova,
M.; Jampilek, J.; Cermak, P.; Kunes, J.; Dolezal, M.; Staud, F. Bioorg. Med. Chem.
2006, 14, 5850–5865; (g) Gong, B.; Hong, F.; Kohm, C.; Bonham, L.; Klein, P.
Bioorg. Med. Chem. Lett. 2004, 14, 1455–1459.
22. General experimental procedure for enzymatic synthesis of 2-substituted
benzothiazoles: In
(0.1 mmol), aldehyde (0.1 mmol), and 0.5 ml citrate buffer (pH 6.0) were
taken and stirred for 10 min. Then, -glucose (0.2 mmol in 0.5 ml), Glucose
a
25 ml round-bottomed flask, 2-aminothiophenol
D
oxidase, Chlorooxidase, and citrate buffer (pH 6.0) were taken and stirred for
12 h under oxygen atmosphere. The reaction was followed by TLC monitoring.
After completion of the reaction, the crude was extracted with ethyl acetate
and the organic phase was evaporated. The solid obtained was recrystallized
from methanol. Spectral data for 2-phenylbenzo[d]thiazoles. Physical state:
solid Rf = 0.47 (1/9 ethyl acetate/hexanes). ESI-MS (m/z) = 212.2 (M+H)+. 1H
NMR (300 MHz, CDCl3) d 8.05–8.16 (m, 3H), 7.92 (d, J = 8.0 Hz, 1H), 7.42–7.53
(m, 4H), 7.39 (d, J = 8.0 Hz, 1H). Anal. Calcd for C13H9NS: C, 73.90; H, 4.29; N,
6.63. Found: C, 73.83; H, 4.33; N, 6.65. Spectral data for 2-
phenylbenzo[d]oxazoles. Physical state: solid Rf = 0.43 (1/9 ethyl acetate/
hexanes). ESI-MS (m/z) = 196.1 (M+H)+. 1H NMR (CDCl3, 300 MHz): d = 8.25–
8.30 (m, 2H), 7.75–7.80 (m, 1H), 7.50–7.56 (m, 3H), 7.58–7.68 (m, 1H), 7.33–
7.40 (m, 2H). Anal. Calcd for C13H9NO: C, 79.98; H, 4.65; N, 7.17. Found: C,
79.94; H, 4.58; N, 7.25.
2. Kashiyama, E.; Hutchinson, I.; Chua, M. S.; Stinson, S. F.; Phillips, L. R.; Kaur, G.;
Sausville, E. A.; Bradshaw, T. D.; Westwell, A. D.; Stevens, M. F. G. J. Med. Chem.
1999, 42, 4172.
3. (a) Mathis, C. A.; Wang, Y.; Holt, D. P.; Huang, G.-F.; Debnath, M. L.; Klunk, W. E.
J. Med. Chem. 2003, 46, 2740; (b) Hutchinson, I.; Jennings, S. A.; Vishnuvajjala, B.
R.; Westwell, A. D.; Stevens, M. F. G. J. Med. Chem. 2002, 45, 744; (c) Alagille, D.;
Baldwin, R. M.; Tamagnan, G. D. Tetrahedron Lett. 2005, 46, 1349; (d) Caujolle,
R.; Loiseau, P.; Payard, M.; Gayral, P.; Kerhir, M. N. Ann. Pharm. Fr. 1989, 47, 68;
(e) Yamamoto, K.; Fujita, M.; Tabashi, K.; Kawashima, Y.; Kato, E.; Oya, M.; Iso,
T.; Iwao, J. J. Med. Chem. 1988, 31, 919; (f) Yoshida, H.; Nakao, R.; Nohta, H.;
Yamaguchi, M. Dyes Pigments 2000, 47, 239.