Regioselective trapping of terminal di-, tri-, and tetraynes with benzyl azide

Organic Letters

Volumn 8, Issue 26, 2006, Pages 6035-6038

  Luu, Thanh ^a   McDonald, Robert ^a   Tykwinski, Rik R ^a  

^a UNIVERSITY OF ALBERTA   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 33846154615     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol062522a     Document Type: Article

References (25)

1. (a) Shi Shun, A. L. K.; Tykwinski, R. R. Angew. Chem., Int. Ed. 2006, 45, 1034-1057.
2. (b) Bohlmann, F.; Burkhardt, H.; Zdero, C. Naturally Occurring Acetylenes; Academic Press: New York, 1973.
3. (c) Chemistry Biology of Naturally Occurring Acetylenes and Related Compounds (NOARC); Lam, J., Breteler, H., Arnason, T., Hansen, L., Eds.; Elsevier: New York, 1988.
4. (d) Jones, E. R.; Thaller, V. The Chemistry of the Carbon-Carbon Triple Bond; Patai, S., Ed.; John Wiley & Sons: New York, 1978; Vol. Part 2, Chapter 14.
5. Some terminal diynes are, however, surprisingly stable. For examples, see: West, K.; Wang, C.; Batsanov, A. S.; Bryce, M. R. J. Org. Chem. 2006, 71, 8541-8544.
6. Jones, E. R. H.; Stephenson, J. S. J. Chem. Soc. 1959, 2197-2203.
7. Kusumi, T.; Ohtani, I.; Nishiyama, K.; Kakisawa, H. Tetrahedron Lett. 1987, 28, 3981-3984.
8. Bittner, M.; Jakupovic, J.; Bohlmann, F.; Silva, M. Phytochemistry 1989, 28, 271-273.
9. For a recent review, see: Bock, V. D.; Hiemstra, H.; van Maarseveen, J. H. Eur. J. Org. Chem. 2006, 51-68.
10. To our knowledge, the reaction of terminal tri- or tetraynes with azides under Cu(I) catalysis has not been explored, whereas one example exists for the reaction with a terminal diyne. See: Reck, F.; Zhou, F.; Girardot, M.; Kern, G.; Eyermann, C. J.; Hales, N. J.; Ramsay, R. R.; Gravestock, M. B. J. Med. Chem. 2005, 48, 499-506.
11. For a recent report that may involve the reaction of an internal diyne with azides under similar conditions to give ethynyl triazoles, see: Gerard, B.; Ryan, J.; Beeler, A. B.; Porco, J. A., Jr. Tetrahedron 2006, 62, 6405-6411.
12. Rostovtsev, V. V.; Green, L. G.; Fokin, V. V.; Sharpless, K. B. Angew. Chem., Int. Ed. 2002, 41, 2596-2599.
13. (a) Lee, L. V.; Mitchell, M. L.; Huang, S.-J.; Folkin, V. V.; Sharpless, K. B.; Wong, C.-H. J. Am. Chem. Soc. 2003, 125, 9588-9589.
14. (b) Aucagne, V.; Leigh, D. A. Org. Lett. 2006, 8, 4505-4507.
15. (c) Pirali, T.; Iron, G. C.; Zhu, J. Org. Lett. 2006, 8, 4145-4148.
16. (d) Lee, J. W.; Kim, B.-K. Bull. Korean Chem. Soc. 2005, 26, 658-660.
17. The thermal reaction of terminal diynes with benzyl azide affords some bisadduct. See: Tikhonova, L. G.; Serebryakova, E. S.; Proidakov, A. G.; Sokolova, I. E.; Vereshchagin, L. I. J. Org. Chem. USSR 1981, 17, 645-648.
18. 3 was used, whereas for triynes, slightly less was used (ca. 0.7-0.8 equiv) due to increasing material losses observed during the desilylation process. See Supporting Information for details.
19. Bohlmann, F.; Arnt, C.; Bornowski, H.; Kleine, K.-M.; Herbst, P. Chem. Ber. 1964, 97, 1179-1192.
20. Hearn, M. T. W.; Jones, E. R. H.; Pellatt, M. G.; Thaller, V.; Turner, S. L. J. Chem. Soc., Perkin Trans. 1 1973, 2785-2788.
21. Caution! Phenylhexatriyne has been reported to explode upon attempted isolation. See: Armitage, J. B.; Entwistle, N.; Jones, E. R. H.; Whiting, M. C. J. Chem. Soc. 1954, 147-154. Although we have never had any problems with explosive decomposition of terminal di-, tri-, or tetraynes under the reaction conditions described, care should nonetheless be taken.
22. Cambie, R. C.; Hirschberg, A.; Jones, E. R. H.; Lowe, G. J. Chem. Soc. 1963, 4120-4130.
23. Bettison, R. M.; Hitchcock, P. B.; Walton, D. R. M. J. Organomet. Chem. 1988, 341, 247-254.
24. 2); CCDC 623597. X-ray data have been deposited at the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB21EZ, UK; fax: (+44)1223-336-033.
25. Only three structures of ethynyltriazole derivatives were found in the CCDC (GIRMUP, GIRNAW, TUGVEW), and none were derived from terminal polyynes. See ref 16 and: Adamson, G. A.; Rees, C. W. J. Chem. Soc., Perkin Trans. 1 1996, 1535-1543.