Synthesis of highly substituted indolines and indoles via intramolecular [4 + 2] cycloaddition of ynamides and conjugated enynes

Journal of the American Chemical Society

Volumn 127, Issue 16, 2005, Pages 5776-5777

  Dunetz, Joshua R ^a   Danheiser, Rick L ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AMIDE; ENYNAMIDE; INDOLE DERIVATIVE; INDOLINE; UNCLASSIFIED DRUG; YNAMIDE;

ADDITION REACTION; ARTICLE; CHEMICAL ANALYSIS; CYCLIZATION; DRUG STRUCTURE; DRUG SYNTHESIS; INTRAMOLECULAR CYCLOADDITION; OXIDATION; POLYMERIZATION;

ALKYNES; AMIDES; CYCLIZATION; INDOLES;

EID: 17744371152     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja051180l     Document Type: Article

References (23)

1. For reviews of indole and indoline chemistry, see: (a) Joule, J. A. In Science of Synthesis; Thomas, E. J., Ed.; Thieme: Stuttgart, 2000; Vol. 10, pp 361-652. (b) Sundberg, R. J. Indoles; Academic Press: London, 1996.
2. For reviews of indole and indoline chemistry, see: (a) Joule, J. A. In Science of Synthesis; Thomas, E. J., Ed.; Thieme: Stuttgart, 2000; Vol. 10, pp 361-652. (b) Sundberg, R. J. Indoles; Academic Press: London, 1996.
3. For examples of the synthesis of indoles and indolines via intramolecular [4 + 2] cycloadditions, see: (a) Boger, D. L.; Coleman, R. S. J. Org. Chem. 1984, 49, 2240. (b) Hayakawa, K.; Yasukouchi, T.; Kanematsu, K. Tetrahedron Lett. 1986, 27, 1837. (c) Padwa, A.; Brodney, M. A.; Liu, B.; Satake, K.; Wu, T. J. Org. Chem. 1999, 64, 3595. (d) Witulski, B.; Lumtscher, J.; Bergsträsser, U. Synlett 2003, 708.
4. For examples of the synthesis of indoles and indolines via intramolecular [4 + 2] cycloadditions, see: (a) Boger, D. L.; Coleman, R. S. J. Org. Chem. 1984, 49, 2240. (b) Hayakawa, K.; Yasukouchi, T.; Kanematsu, K. Tetrahedron Lett. 1986, 27, 1837. (c) Padwa, A.; Brodney, M. A.; Liu, B.; Satake, K.; Wu, T. J. Org. Chem. 1999, 64, 3595. (d) Witulski, B.; Lumtscher, J.; Bergsträsser, U. Synlett 2003, 708.
5. For examples of the synthesis of indoles and indolines via intramolecular [4 + 2] cycloadditions, see: (a) Boger, D. L.; Coleman, R. S. J. Org. Chem. 1984, 49, 2240. (b) Hayakawa, K.; Yasukouchi, T.; Kanematsu, K. Tetrahedron Lett. 1986, 27, 1837. (c) Padwa, A.; Brodney, M. A.; Liu, B.; Satake, K.; Wu, T. J. Org. Chem. 1999, 64, 3595. (d) Witulski, B.; Lumtscher, J.; Bergsträsser, U. Synlett 2003, 708.
6. For examples of the synthesis of indoles and indolines via intramolecular [4 + 2] cycloadditions, see: (a) Boger, D. L.; Coleman, R. S. J. Org. Chem. 1984, 49, 2240. (b) Hayakawa, K.; Yasukouchi, T.; Kanematsu, K. Tetrahedron Lett. 1986, 27, 1837. (c) Padwa, A.; Brodney, M. A.; Liu, B.; Satake, K.; Wu, T. J. Org. Chem. 1999, 64, 3595. (d) Witulski, B.; Lumtscher, J.; Bergsträsser, U. Synlett 2003, 708.
7. (a) Danheiser, R. L.; Gould, A. E.; Fernández de la Pradilla, R.; Helgason, A. L. J. Org. Chem. 1994, 59, 5514.
8. (b) Wills, M. S. B.; Danheiser, R. L. J. Am. Chem. Soc. 1998, 120, 9378 and references therein.
9. For related cycloadditions of conjugated arenynes (the "Michael-Bucher reaction"), see Rodríguez, D.; Martínez-Esperón, M. F.; Navarro-Vázquez, A.; Castedo, L.; Domínguez, D.; Saá, C. J. Org. Chem. 2004, 69, 3842 and references therein.
10. For reviews of transition-metal-catalyzed enyne cycloadditions, see: (a) Rubin, M.; Sromek, A. W.; Gevorgyan, V. Synlett 2003, 2265. (b) Saito, S.; Yamamoto, Y. Chem. Rev. 2000, 100, 2901.
11. For reviews of transition-metal-catalyzed enyne cycloadditions, see: (a) Rubin, M.; Sromek, A. W.; Gevorgyan, V. Synlett 2003, 2265. (b) Saito, S.; Yamamoto, Y. Chem. Rev. 2000, 100, 2901.
12. For reviews of ynamide chemistry, see: (a) Mulder, J. A.; Kurtz, K. C. M.; Hsung, R. P. Synlett 2003, 1379. (b) Zificsak, C. A.; Mulder, J. A.; Hsung, R. P.; Rameshkumar, C.; Wei, L.-L. Tetrahedron 2001, 57, 7575.
13. For reviews of ynamide chemistry, see: (a) Mulder, J. A.; Kurtz, K. C. M.; Hsung, R. P. Synlett 2003, 1379. (b) Zificsak, C. A.; Mulder, J. A.; Hsung, R. P.; Rameshkumar, C.; Wei, L.-L. Tetrahedron 2001, 57, 7575.
14. For mechanistic and theoretical studies on enyne and arenyne cycloadditions, see: (a) Burrell, R. C.; Daoust, K. J.; Bradley, A. Z.; DiRico, K. J.; Johnson, R. P. J. Am. Chem. Soc. 1996, 118, 4218. (b) Ananikov, V. P. J. Phys. Org. Chem. 2001, 14, 109. (c) Rodríguez, D.; Navarro- Vázquez, A.; Castedo, L.; Domínguez, D.; Saá, C. J. Org. Chem. 2003, 68, 1938.
15. For mechanistic and theoretical studies on enyne and arenyne cycloadditions, see: (a) Burrell, R. C.; Daoust, K. J.; Bradley, A. Z.; DiRico, K. J.; Johnson, R. P. J. Am. Chem. Soc. 1996, 118, 4218. (b) Ananikov, V. P. J. Phys. Org. Chem. 2001, 14, 109. (c) Rodríguez, D.; Navarro- Vázquez, A.; Castedo, L.; Domínguez, D.; Saá, C. J. Org. Chem. 2003, 68, 1938.
16. For mechanistic and theoretical studies on enyne and arenyne cycloadditions, see: (a) Burrell, R. C.; Daoust, K. J.; Bradley, A. Z.; DiRico, K. J.; Johnson, R. P. J. Am. Chem. Soc. 1996, 118, 4218. (b) Ananikov, V. P. J. Phys. Org. Chem. 2001, 14, 109. (c) Rodríguez, D.; Navarro- Vázquez, A.; Castedo, L.; Domínguez, D.; Saá, C. J. Org. Chem. 2003, 68, 1938.
17. Dunetz, J. R.; Danheiser, R. L. Org. Lett. 2003, 5, 4011.
18. Alternative N-alkynylation methods catalytic in copper require elevated temperatures and were not suitable for the preparation of these cycloaddition substrates. See: (a) Zheng, Y.; Hsung, R. P.; Tracey, M. R.; Kurtz, K. C. M.; Vera, E. L. Org. Lett. 2004, 6, 1151. (b) Frederick, M. O.; Mulder, J. A.; Tracey, M. R.; Hsung, R. P.; Huang, J.; Kurtz, K. C. M.; Shen, L.; Douglas, C. J. J. Am. Chem. Soc. 2003, 125, 2368.
19. Alternative N-alkynylation methods catalytic in copper require elevated temperatures and were not suitable for the preparation of these cycloaddition substrates. See: (a) Zheng, Y.; Hsung, R. P.; Tracey, M. R.; Kurtz, K. C. M.; Vera, E. L. Org. Lett. 2004, 6, 1151. (b) Frederick, M. O.; Mulder, J. A.; Tracey, M. R.; Hsung, R. P.; Huang, J.; Kurtz, K. C. M.; Shen, L.; Douglas, C. J. J. Am. Chem. Soc. 2003, 125, 2368.
20. The N-sulfonyl ynamides 6-9 were prepared by alkynylation with alkynyl-(phenyl)iodonium salts. See: Witulski, B.; Stengel, T. Angew. Chem., Int. Ed. 1998, 37, 489.
21. 2OMe) were found to proceed in poor yield.
22. See ref 1 and (a) Zhang, D.; Liebeskind, L. S. J. Org. Chem. 1996, 61, 2594. (b) Bailey, W. F.; Jiang, X.-L. J. Org. Chem. 1996, 61, 2596.
23. See ref 1 and (a) Zhang, D.; Liebeskind, L. S. J. Org. Chem. 1996, 61, 2594. (b) Bailey, W. F.; Jiang, X.-L. J. Org. Chem. 1996, 61, 2596.