Extension of the Eschenmoser sulfide contraction/iminoester cyclization method to the synthesis of tolyporphin chromophore

Tetrahedron Letters

Volumn 38, Issue 39, 1997, Pages 6811-6814

  Minehan, Thomas G ^a   Kishi, Yoshito ^a  

^a HARVARD UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

PORPHYRIN DERIVATIVE; TOLPORPHYRIN; UNCLASSIFIED DRUG;

ARTICLE; CYCLIZATION; DRUG SYNTHESIS; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; REACTION ANALYSIS;

EID: 0030752083     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(97)01601-8     Document Type: Article

References (24)

1. Prinsep, M. R.; Caplan, F. R.; Moore, R. E.; Patterson, G. M.; Smith, C. D. J. Am. Chem. Soc. 1992, 114, 385.
2. The numbering used in this paper corresponds to that of tolyporphin.
3. For recent reviews on MDR, see: (a) Pastan, I.; Gottesman, M. M. Ann. Rev. Biochem. 1993, 62, 385.
4. (b) Simon, S. M.; Schindler, M. Proc. Natl. Acad. Sci. USA 1994, 91, 3497.
5. For further examples of MDR reversing agents, see: (a) Ghosh, A. K.; Liu, W.; Xu, Y.; Chen, Z. Angew. Chem. Int. Ed. Engl. 1996, 35, 74.
6. (b) Andrus, M. B.; Lepore, S. D. J. Am. Chem. Soc. 1997, 119, 2327.
7. For reviews of the sulfide contraction method, see: (a) Eschenmoser, A. Quart. Rev. Chem. Soc. 1970, 24, 366.
8. (b) Roth, M.; Dobs, E.; Gotschi, E.; Eschenmoser, A. Helv. Chim. Acta. 1971, 54, 710.
9. (a) Johnson, A. P.; Wehrli, P.; Fletcher, R.; Eschenmoser, A. Angew. Chem. internat. Ed. Engl. 1968, 7, 623.
10. (b) Gotschi, E.; Hunkeler, W.; Wild, H. J.; Schneider, P.; Fuhrer, W.; Gleason, J.; Eschenmoser, A. Angew. Chem. internat. Ed. Engl. 1973, 11, 910.
11. (c) Muller, P. M.; Farooq, S.; Hardegger, W.; Salmond, S.; Eschenmoser, A. Angew. Chem. internat. Ed. Engl. 1973, 11, 914.
12. Schwesinger, R.; Waditschatka, R.; Rigby, J.; Nordmann, R.; Schweizer, W. B.; Zass, E.; Eschenmoser, A. Helv. Chim. Acta 1982, 61, 600.
13. For an alternative approach to dioxobacteriochlorins from porphyrins, see Pandey, R. K.; Isaac, M.; MacDonald, I.; Medforth, C. J.; Senge, M. O.; Dougherty, T. J.; Smith, K. M. J. Org. Chem. 1997, 62, 1463.
14. The monocyclic precursors 12 and 14 were synthesized as outlined below. (formula presented) Reagents and conditions: (a) LDA, THF; MeI, -78 °C.
15. 2CO,-78 °C.
16. 2, r.t., 16 h.
17. (d) LAH, THF, r.t.
18. 4, r.t.
19. 3N, THF, r.t.
20. (g) xylenes-azeotrope, 160 °C.
21. 2O, -78 °C→0 °C.
22. Yamada, Y.; Miljkovic, D.; Wehrli, P.; Golding, B.; Loliger, P.; Keese, R.; Müller, K.; Eschenmoser, A. Angew. Chem. internat. Ed. Engl. 1969, 8, 343.
23. Corey, E. J.; Fleet, G. W. J. Tetrahedron Lett. 1973, 4499.
24. 6) δ 13.1 ppm, 23.5, 23.7, 50.0, 50.1, 95.5, 96.9, 97.1, 99.0, 126.5, 127.2, 136.2-137.9 (4 signals), 167.5 (2 signals), 209.6 (2 signals).