Y. Jin et al. / Tetrahedron Letters 43 (2002) 7319–7321
7321
thank Professor Ronald J. Clark of the FSU Chemistry
Department for determination of the X-ray crystal
structure.
References
1. Gordon, A. M. Coordination Chemistry of Macrocyclic
Compounds; Plenum Press: New York, 1979.
2. Jones, M. M. In Coordination Chemistry; Kauffman, G.
B., Ed. ACS Symposium Series 565, American Chemical
Society: Washington DC, 1994; Chapter 35, pp. 427–438.
3. Bernado, M. M.; Brown, S.; Li, Z.; Fridman, R.;
Mobashery, S. J. Biol. Chem. 2002, 277, 11201–11207.
4. Sang, Q. X. A.; Schwartz, M. A.; Li, H.; Chung, L. W.
K.; Zhau, H. E. Ann. NY Acad. Sci. 1999, 878, 538–540.
5. Sang, Q. X. A.; Jia, M. C.; Schwartz, M. A.; Jaye, M. C.;
Kleinman, H. K.; Ghaffari, M. A.; Luo, Y. L. Biochem.
Biophys. Res. Commun. 2000, 274, 780–786.
6. Willett, J. D.; Grunwell, J. R.; Berchtold, G. A. J. Org.
Chem. 1968, 33, 2297–2302.
7. Petrova, R. G.; Freidlina, R. K. Bull. Acad. Sci. USSR
Div. Chem. Sci. (Engl. Transl.) 1975, 24, 1686–1689.
8. Yoshida, Y.; Sakakura, Y.; Aso, N.; Okada, S.; Tanabe,
Y. Tetrahedron 1999, 55, 2183–2192.
9. Volante, R. P. Tetrahedron Lett. 1981, 22, 3119–3122.
10. Fried, J.; Mehra, M. M.; Chan, Y. Y. J. Am. Chem. Soc.
1974, 96, 6759–6761.
Figure 2. X-Ray crystal structure of cis-3,4-pyrrolidinedithiol
derivative 19.
Selective cleavage of each of the t-Boc protecting
groups in the cis-3,4-pyrrolidinedithiol derivative 15
was possible.23 Treatment of 15 with dry 2N HCl in
EtOAc at room temperature selectively removed the
N-t-Boc group, while selective cleavage of the S-t-Boc
group in 15 was achieved in 2N NaOH in aqueous
MeOH. Both the N- and S-t-Boc groups could be
removed simultaneously with 3N HCl in AcOH. By
application of these procedures, 15 was transformed
into the matrix metalloproteinase inhibitor precursor
19, the structure and stereochemistry of which was
confirmed by X-ray crystallography (Fig. 2).
11. Goodman, L.; Benitez, A.; Baker, B. R. J. Am. Chem.
Soc. 1958, 80, 1680–1686.
12. Rao, A. S.; Paknikar, S. K.; Kirtane, J. G. Tetrahedron
1983, 39, 2323.
13. Iida, T.; Yamampto, N.; Sasai, H.; Shibasaki, M. J. Am.
Chem. Soc. 1997, 119, 4783–4784.
14. Rosowsky, A. In Hetereocyclic Compounds. Part I;
Weissberger, A., Ed.; John Wiley and Sons: New York,
1964; p. 330.
15. Brittain, J.; Gareau, Y. Tetrahedron 1993, 34, 3363–3366.
16. Justo de Pomar, J. C.; Soderquist, J. A. Tetrahedron
1998, 39, 4409–4412.
17. Bean, M.; Kohn, H. J. Org. Chem. 1983, 48, 5033–5041.
18. Posner, G. H.; Rogers, D. Z. J. Am. Chem. Soc. 1977, 99,
8208–8214.
19. Harrak, Y.; Pujol, M. D. Tetrahedron Lett. 2002, 43,
819–822.
General procedure for alumina-mediated epoxide ring-
opening with thiolacids. To a stirred slurry of 36 g of
alumina in 30 mL of dry ether was added the thiolacid
(25 mmol). After 10 min the epoxide (5 mmol) was
added and stirring was continued at rt for 2 h. The
mixture was filtered and the alumina was washed sev-
eral times with ether until nothing else was eluted (TLC
analysis). The combined filtrate was extracted with
saturated aqueous NaHCO3, then was dried over
Na2SO4 and evaporated to give the trans-b-hydroxy-
thioesters which were used without further purifica-
tion.
20. Okada, T.; Sato, H.; Tsuji, T.; Tsushima, T.; Nakai, H.;
Yoshida, T.; Matsuura, S. Chem. Pharm. Bull. 1993, 41,
132–138.
21. The use of thiolacetic acid gave similar results.
22. Prepared from L-Leu by the procedure of: Yankeelov, J.
A., Jr.; Fok, K.-F.; Carothers, D. J. J. Org. Chem. 1978,
43, 1623–1624.
Acknowledgements
23. Muraki, M.; Mizoguchi, T. Chem. Pharm. Bull. 1971, 19,
1708–1713.
Support of this work by a grant from the MDS
Research Foundation is gratefully acknowledged. We