Synthesis, structure, and reactivity of enediyne macrocycles

Journal of Organic Chemistry

Volumn 61, Issue 13, 1996, Pages 4258-4261

  König, Burkhard ^a   Pitsch, Wolfgang ^a   Thondorf, Iris ^b  

^a TECHNICAL UNIVERSITY OF BRAUNSCHWEIG   (Germany)

^b MARTIN LUTHER UNIVERSITY HALLE WITTENBERG   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0041488338     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9600971     Document Type: Article

References (34)

1. For a recent review of nonenzymatic DNA cleavage see: (a) Pratviel, G.; Bernadou, J.; Meunier, B. Angew. Chem. 1995, 107, 819-845; Angew. Chem., Int. Ed. Engl. 1995 34, 746-769. Reviews of enediyne prodrug synthesis: (b) Maier, M. E. Synlett 1995, 13-26. (c) Nicolaou, K. C.; Dai, W.-M. Angew. Chem. 1991, 103, 1453-1481; Angew. Chem., Int. Ed. Engl. 1991, 30, 1387-1415.
2. For a recent review of nonenzymatic DNA cleavage see: (a) Pratviel, G.; Bernadou, J.; Meunier, B. Angew. Chem. 1995, 107, 819-845; Angew. Chem., Int. Ed. Engl. 1995 34, 746-769. Reviews of enediyne prodrug synthesis: (b) Maier, M. E. Synlett 1995, 13-26. (c) Nicolaou, K. C.; Dai, W.-M. Angew. Chem. 1991, 103, 1453-1481; Angew. Chem., Int. Ed. Engl. 1991, 30, 1387-1415.
3. For a recent review of nonenzymatic DNA cleavage see: (a) Pratviel, G.; Bernadou, J.; Meunier, B. Angew. Chem. 1995, 107, 819-845; Angew. Chem., Int. Ed. Engl. 1995 34, 746-769. Reviews of enediyne prodrug synthesis: (b) Maier, M. E. Synlett 1995, 13-26. (c) Nicolaou, K. C.; Dai, W.-M. Angew. Chem. 1991, 103, 1453-1481; Angew. Chem., Int. Ed. Engl. 1991, 30, 1387-1415.
4. For a recent review of nonenzymatic DNA cleavage see: (a) Pratviel, G.; Bernadou, J.; Meunier, B. Angew. Chem. 1995, 107, 819-845; Angew. Chem., Int. Ed. Engl. 1995 34, 746-769. Reviews of enediyne prodrug synthesis: (b) Maier, M. E. Synlett 1995, 13-26. (c) Nicolaou, K. C.; Dai, W.-M. Angew. Chem. 1991, 103, 1453-1481; Angew. Chem., Int. Ed. Engl. 1991, 30, 1387-1415.
5. For a recent review of nonenzymatic DNA cleavage see: (a) Pratviel, G.; Bernadou, J.; Meunier, B. Angew. Chem. 1995, 107, 819-845; Angew. Chem., Int. Ed. Engl. 1995 34, 746-769. Reviews of enediyne prodrug synthesis: (b) Maier, M. E. Synlett 1995, 13-26. (c) Nicolaou, K. C.; Dai, W.-M. Angew. Chem. 1991, 103, 1453-1481; Angew. Chem., Int. Ed. Engl. 1991, 30, 1387-1415.
6. Selected examples of various trigger mechanisms. Bioreduction: (a) Semmelhack, M. F.; Gallagher, J.; Cohen, D. Tetrahedron Lett. 1990, 3;, 1521-1522. Photochemical: (b) Nakatani, K.; Isoe, S.; Maekawa, S.; Saito, I. Tetrahedron Lett. 1994, 35, 605-608. (c) Nuss, J. M.; Murphy, M. M. Tetrahedron Lett. 1994, 35, 37-40. Base induced: (d) Kerwin, S. M. Tetrahedron Lett. 1994, 35, 1023-1026. (e) Wu, M.-J.; Lin, C.-F.; Wu, J.-S.; Chen, H.-T. Tetrahedron Lett. 1994, 35, 1879-1882. Metal ion induced: (f) Warner, B. P.; Millar, S. P.; Broene, R. D.; Buchwald, S. L. Science 1995, 269, 814-816.
7. Selected examples of various trigger mechanisms. Bioreduction: (a) Semmelhack, M. F.; Gallagher, J.; Cohen, D. Tetrahedron Lett. 1990, 3;, 1521-1522. Photochemical: (b) Nakatani, K.; Isoe, S.; Maekawa, S.; Saito, I. Tetrahedron Lett. 1994, 35, 605-608. (c) Nuss, J. M.; Murphy, M. M. Tetrahedron Lett. 1994, 35, 37-40. Base induced: (d) Kerwin, S. M. Tetrahedron Lett. 1994, 35, 1023-1026. (e) Wu, M.-J.; Lin, C.-F.; Wu, J.-S.; Chen, H.-T. Tetrahedron Lett. 1994, 35, 1879-1882. Metal ion induced: (f) Warner, B. P.; Millar, S. P.; Broene, R. D.; Buchwald, S. L. Science 1995, 269, 814-816.
8. Selected examples of various trigger mechanisms. Bioreduction: (a) Semmelhack, M. F.; Gallagher, J.; Cohen, D. Tetrahedron Lett. 1990, 3;, 1521-1522. Photochemical: (b) Nakatani, K.; Isoe, S.; Maekawa, S.; Saito, I. Tetrahedron Lett. 1994, 35, 605-608. (c) Nuss, J. M.; Murphy, M. M. Tetrahedron Lett. 1994, 35, 37-40. Base induced: (d) Kerwin, S. M. Tetrahedron Lett. 1994, 35, 1023-1026. (e) Wu, M.-J.; Lin, C.-F.; Wu, J.-S.; Chen, H.-T. Tetrahedron Lett. 1994, 35, 1879-1882. Metal ion induced: (f) Warner, B. P.; Millar, S. P.; Broene, R. D.; Buchwald, S. L. Science 1995, 269, 814-816.
9. Selected examples of various trigger mechanisms. Bioreduction: (a) Semmelhack, M. F.; Gallagher, J.; Cohen, D. Tetrahedron Lett. 1990, 3;, 1521-1522. Photochemical: (b) Nakatani, K.; Isoe, S.; Maekawa, S.; Saito, I. Tetrahedron Lett. 1994, 35, 605-608. (c) Nuss, J. M.; Murphy, M. M. Tetrahedron Lett. 1994, 35, 37-40. Base induced: (d) Kerwin, S. M. Tetrahedron Lett. 1994, 35, 1023-1026. (e) Wu, M.-J.; Lin, C.-F.; Wu, J.-S.; Chen, H.-T. Tetrahedron Lett. 1994, 35, 1879-1882. Metal ion induced: (f) Warner, B. P.; Millar, S. P.; Broene, R. D.; Buchwald, S. L. Science 1995, 269, 814-816.
10. Selected examples of various trigger mechanisms. Bioreduction: (a) Semmelhack, M. F.; Gallagher, J.; Cohen, D. Tetrahedron Lett. 1990, 3;, 1521-1522. Photochemical: (b) Nakatani, K.; Isoe, S.; Maekawa, S.; Saito, I. Tetrahedron Lett. 1994, 35, 605-608. (c) Nuss, J. M.; Murphy, M. M. Tetrahedron Lett. 1994, 35, 37-40. Base induced: (d) Kerwin, S. M. Tetrahedron Lett. 1994, 35, 1023-1026. (e) Wu, M.-J.; Lin, C.-F.; Wu, J.-S.; Chen, H.-T. Tetrahedron Lett. 1994, 35, 1879-1882. Metal ion induced: (f) Warner, B. P.; Millar, S. P.; Broene, R. D.; Buchwald, S. L. Science 1995, 269, 814-816.
11. Selected examples of various trigger mechanisms. Bioreduction: (a) Semmelhack, M. F.; Gallagher, J.; Cohen, D. Tetrahedron Lett. 1990, 3;, 1521-1522. Photochemical: (b) Nakatani, K.; Isoe, S.; Maekawa, S.; Saito, I. Tetrahedron Lett. 1994, 35, 605-608. (c) Nuss, J. M.; Murphy, M. M. Tetrahedron Lett. 1994, 35, 37-40. Base induced: (d) Kerwin, S. M. Tetrahedron Lett. 1994, 35, 1023-1026. (e) Wu, M.-J.; Lin, C.-F.; Wu, J.-S.; Chen, H.-T. Tetrahedron Lett. 1994, 35, 1879-1882. Metal ion induced: (f) Warner, B. P.; Millar, S. P.; Broene, R. D.; Buchwald, S. L. Science 1995, 269, 814-816.
12. Brandstetter, T.; Maier, M. E. Tetrahedron 1994, 50, 1435-1448.
13. Preliminary communication on the activation of enediyne macrocycles by metal ion coordination: König, B.; Hollnagel, H.; Ahrens, B.; Jones, P. G. Angew. Chem. 1995, 107, 2763-2765; Angew. Chem. Int. Ed. Engl. 1995, 34, 2538-2540.
14. Preliminary communication on the activation of enediyne macrocycles by metal ion coordination: König, B.; Hollnagel, H.; Ahrens, B.; Jones, P. G. Angew. Chem. 1995, 107, 2763-2765; Angew. Chem. Int. Ed. Engl. 1995, 34, 2538-2540.
15. (a) König, B.; Pitsch, W.; Dix, I.; Jones, P. G. Synthesis 1996, 446-448.
16. (b) See supporting information for the preparation of functionalized acyclic enediynes 5g-1 by reaction of 4 with nucleophiles.
17. Brandsma, L.; Verkruijsse, H. Preparative Polar Organometallic Chemistry 1; Springer: Berlin, 1990; p 79 ff.
18. Hegedus, L. S. In Organometallics in Synthesis; Schlosser, M., d.; Wiley: Chichester, 1994; p 383 ff.
19. Schwarz, M.; Oliver, J. E.; Sonnet, P. E. J. Org. Chem. 1975, 40, 2410-2411.
20. Elias, H.-G. Makromoleküle, Bd. 1; Hüthig & Wepf: Basel, 1990; p 817-820.
21. 2 log k = 7.1.
22. Examples of conformational control by metal ion coordination: (a) Kelly, T. R.; Bowyer, M. C.; Bhaskar, K. V.; Bebbington, D.; Garcia, A.; Lang, F.; Kim, M. H.; Jette, M. P. J. Am. Chem. Soc. 1994, 116, 3657-3658. (b) Rebek, J., Jr.; Wattley, R. V. J. Heterocycl. Chem. 1980, 17, 749-751. (c) Rebek, J., Jr.; Wattley, R. V. J. Am. Chem. Soc. 1980, 102, 4853-4854.
23. Examples of conformational control by metal ion coordination: (a) Kelly, T. R.; Bowyer, M. C.; Bhaskar, K. V.; Bebbington, D.; Garcia, A.; Lang, F.; Kim, M. H.; Jette, M. P. J. Am. Chem. Soc. 1994, 116, 3657-3658. (b) Rebek, J., Jr.; Wattley, R. V. J. Heterocycl. Chem. 1980, 17, 749-751. (c) Rebek, J., Jr.; Wattley, R. V. J. Am. Chem. Soc. 1980, 102, 4853-4854.
24. Examples of conformational control by metal ion coordination: (a) Kelly, T. R.; Bowyer, M. C.; Bhaskar, K. V.; Bebbington, D.; Garcia, A.; Lang, F.; Kim, M. H.; Jette, M. P. J. Am. Chem. Soc. 1994, 116, 3657-3658. (b) Rebek, J., Jr.; Wattley, R. V. J. Heterocycl. Chem. 1980, 17, 749-751. (c) Rebek, J., Jr.; Wattley, R. V. J. Am. Chem. Soc. 1980, 102, 4853-4854.
25. (a) All calculations have been performed on a SGI Crimson VGXT workstation with the MM3(94) force field: Allinger, N. L.; Yuh, Y. H.; Lii, J.-H. J. Am. Chem. Soc. 1989, 111, 8551-8566.
26. (b) Lii, J.-H.; Allinger, N. L. Ibid. 8566-8575.
27. (c) Lii, J.-H.; Allinger, N. L. Ibid. 8566-8575.
28. (d) For the notation of calixarene conformations see: Gutsche, C. D. Calixarenes; Monographs in Supramolecular Chemistry; Stoddart, J. F., Ed.; The Royal Society of Chemistry: Cambridge, 1992.
29. 3) was heated in decalin or ethylene glycol the hydrogen trapped product of the Bergman cyclization 6 could be identified by NMR, high resolution mass spectra, and TLC. The compound was synthesized independently for comparison from 3,3′-dihydroxy-6,6′-dimethyl-2,2′-bipyridine and α,α′-dibromo-o-xylylene. See supporting information for details.
30. With the assumption of the same rate of reaction at the given cyclization temperatures, a 20% decrease in activation energy by the induced conformation change can be estimated.
31. To investigate the possible influence of the morphology of the solids on their reactivity, DSCs were recorded from single crystals and powders of 5b. The observed temperatures of the exothermic cyclization are identical.
32. The simple NMR spectra of 5d suggest either a single conformer of high symmetry or rapid interconversion between conformers at room temperature.
33. The reactivity of highly strained [7.3.1]enediynes is very sensitive to small conformational changes; ref 1b.
34. Compounds 5e and 5f have been characterized by X-ray structure analysis: Jones, P. G.; Dix, I. Unpublished results.