Catalytic alkynylation of ketones and aldehydes using quaternary ammonium hydroxide base

Journal of Organic Chemistry

Volumn 68, Issue 9, 2003, Pages 3702-3705

  Ishikawa, Teruhiko ^a   Mizuta, Tomohiro ^b   Hagiwara, Kumiko ^b   Aikawa, Toshiaki ^b   Kudo, Takayuki ^b   Saito, Seiki ^b  

^a OKAYAMA UNIVERSITY   (Japan)

^b School of Engineering   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ALDEHYDES; CATALYSTS; CHEMICAL BONDS; CHEMICAL REACTIONS; RESINS;

CATALYTIC ALKYNYLATION;

KETONES;

ALDEHYDE; HYDROXIDE; KETONE; QUATERNARY AMMONIUM DERIVATIVE;

ARTICLE; CATALYSIS; CHEMICAL MODIFICATION; CHEMICAL REACTION; CHEMICAL STRUCTURE; REACTION ANALYSIS;

EID: 0037414541     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo026592g     Document Type: Article

References (23)

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7. For quaternary ammonium hydroxide-catalyzed reactions, (a) O'Donnell, M. J.; Bennett, W. D.; Wu, S. J. Am. Chem. Soc. 1989, 111, 2353-2355. (b) Arai, S.; Shirai, Y. Ishida, T.; Shioiri, T. Chem. Commun. 1999, 49-50. (c) Corey, E. J.; Bo, Y.; Petersen, J. B. J. Am. Chem. Soc. 1998, 120, 13000-13001. For other nonmetal organo-catalytic processes (d) Ooi, T.; Takeuchi, M.; Kameda, M.; Maruoka, K. J. Am. Chem. Soc. 2000, 122, 5228-5229. For other nonmetal organo-catalytic processes. (e) Hajos, Z. G.; Parrish, D. R. J. Org. Chem. 1974, 39, 1615-1621. (f) List, B.; Lerner, R. A.; Barbas, C. F., III. J. Am. Chem. Soc. 2000, 122, 2395-2396. (g) Paras, N. A.; MacMillan, D. W. C. J. Am. Chem. Soc. 2001, 123, 4370-4371.
8. For quaternary ammonium hydroxide-catalyzed reactions, (a) O'Donnell, M. J.; Bennett, W. D.; Wu, S. J. Am. Chem. Soc. 1989, 111, 2353-2355. (b) Arai, S.; Shirai, Y. Ishida, T.; Shioiri, T. Chem. Commun. 1999, 49-50. (c) Corey, E. J.; Bo, Y.; Petersen, J. B. J. Am. Chem. Soc. 1998, 120, 13000-13001. For other nonmetal organo-catalytic processes (d) Ooi, T.; Takeuchi, M.; Kameda, M.; Maruoka, K. J. Am. Chem. Soc. 2000, 122, 5228-5229. For other nonmetal organo-catalytic processes. (e) Hajos, Z. G.; Parrish, D. R. J. Org. Chem. 1974, 39, 1615-1621. (f) List, B.; Lerner, R. A.; Barbas, C. F., III. J. Am. Chem. Soc. 2000, 122, 2395-2396. (g) Paras, N. A.; MacMillan, D. W. C. J. Am. Chem. Soc. 2001, 123, 4370-4371.
9. For quaternary ammonium hydroxide-catalyzed reactions, (a) O'Donnell, M. J.; Bennett, W. D.; Wu, S. J. Am. Chem. Soc. 1989, 111, 2353-2355. (b) Arai, S.; Shirai, Y. Ishida, T.; Shioiri, T. Chem. Commun. 1999, 49-50. (c) Corey, E. J.; Bo, Y.; Petersen, J. B. J. Am. Chem. Soc. 1998, 120, 13000-13001. For other nonmetal organo-catalytic processes (d) Ooi, T.; Takeuchi, M.; Kameda, M.; Maruoka, K. J. Am. Chem. Soc. 2000, 122, 5228-5229. For other nonmetal organo-catalytic processes. (e) Hajos, Z. G.; Parrish, D. R. J. Org. Chem. 1974, 39, 1615-1621. (f) List, B.; Lerner, R. A.; Barbas, C. F., III. J. Am. Chem. Soc. 2000, 122, 2395-2396. (g) Paras, N. A.; MacMillan, D. W. C. J. Am. Chem. Soc. 2001, 123, 4370-4371.
10. For quaternary ammonium hydroxide-catalyzed reactions, (a) O'Donnell, M. J.; Bennett, W. D.; Wu, S. J. Am. Chem. Soc. 1989, 111, 2353-2355. (b) Arai, S.; Shirai, Y. Ishida, T.; Shioiri, T. Chem. Commun. 1999, 49-50. (c) Corey, E. J.; Bo, Y.; Petersen, J. B. J. Am. Chem. Soc. 1998, 120, 13000-13001. For other nonmetal organo-catalytic processes (d) Ooi, T.; Takeuchi, M.; Kameda, M.; Maruoka, K. J. Am. Chem. Soc. 2000, 122, 5228-5229. For other nonmetal organo-catalytic processes. (e) Hajos, Z. G.; Parrish, D. R. J. Org. Chem. 1974, 39, 1615-1621. (f) List, B.; Lerner, R. A.; Barbas, C. F., III. J. Am. Chem. Soc. 2000, 122, 2395-2396. (g) Paras, N. A.; MacMillan, D. W. C. J. Am. Chem. Soc. 2001, 123, 4370-4371.
11. For quaternary ammonium hydroxide-catalyzed reactions, (a) O'Donnell, M. J.; Bennett, W. D.; Wu, S. J. Am. Chem. Soc. 1989, 111, 2353-2355. (b) Arai, S.; Shirai, Y. Ishida, T.; Shioiri, T. Chem. Commun. 1999, 49-50. (c) Corey, E. J.; Bo, Y.; Petersen, J. B. J. Am. Chem. Soc. 1998, 120, 13000-13001. For other nonmetal organo-catalytic processes (d) Ooi, T.; Takeuchi, M.; Kameda, M.; Maruoka, K. J. Am. Chem. Soc. 2000, 122, 5228-5229. For other nonmetal organo-catalytic processes. (e) Hajos, Z. G.; Parrish, D. R. J. Org. Chem. 1974, 39, 1615-1621. (f) List, B.; Lerner, R. A.; Barbas, C. F., III. J. Am. Chem. Soc. 2000, 122, 2395-2396. (g) Paras, N. A.; MacMillan, D. W. C. J. Am. Chem. Soc. 2001, 123, 4370-4371.
12. For quaternary ammonium hydroxide-catalyzed reactions, (a) O'Donnell, M. J.; Bennett, W. D.; Wu, S. J. Am. Chem. Soc. 1989, 111, 2353-2355. (b) Arai, S.; Shirai, Y. Ishida, T.; Shioiri, T. Chem. Commun. 1999, 49-50. (c) Corey, E. J.; Bo, Y.; Petersen, J. B. J. Am. Chem. Soc. 1998, 120, 13000-13001. For other nonmetal organo-catalytic processes (d) Ooi, T.; Takeuchi, M.; Kameda, M.; Maruoka, K. J. Am. Chem. Soc. 2000, 122, 5228-5229. For other nonmetal organo-catalytic processes. (e) Hajos, Z. G.; Parrish, D. R. J. Org. Chem. 1974, 39, 1615-1621. (f) List, B.; Lerner, R. A.; Barbas, C. F., III. J. Am. Chem. Soc. 2000, 122, 2395-2396. (g) Paras, N. A.; MacMillan, D. W. C. J. Am. Chem. Soc. 2001, 123, 4370-4371.
13. For quaternary ammonium hydroxide-catalyzed reactions, (a) O'Donnell, M. J.; Bennett, W. D.; Wu, S. J. Am. Chem. Soc. 1989, 111, 2353-2355. (b) Arai, S.; Shirai, Y. Ishida, T.; Shioiri, T. Chem. Commun. 1999, 49-50. (c) Corey, E. J.; Bo, Y.; Petersen, J. B. J. Am. Chem. Soc. 1998, 120, 13000-13001. For other nonmetal organo-catalytic processes (d) Ooi, T.; Takeuchi, M.; Kameda, M.; Maruoka, K. J. Am. Chem. Soc. 2000, 122, 5228-5229. For other nonmetal organo-catalytic processes. (e) Hajos, Z. G.; Parrish, D. R. J. Org. Chem. 1974, 39, 1615-1621. (f) List, B.; Lerner, R. A.; Barbas, C. F., III. J. Am. Chem. Soc. 2000, 122, 2395-2396. (g) Paras, N. A.; MacMillan, D. W. C. J. Am. Chem. Soc. 2001, 123, 4370-4371.
14. For equilibrium acidity data in DMSO, see: Bordwell, F. G. Acc. Chem. Res. 1988, 21, 456-463.
15. Other products were a mixture of multiple components that were difficult to fractionate, and thus their structures have not been elucidated yet: no starting aldehydes were recovered at all. One definite cause for such low yields observed for aromatic aldehydes should be ascribed to the instability of the products under the given reaction conditions. For example, 4bb led to a complex mixture when exposed to 10 mol % base in DMSO for 2 h at room temperature, although it was kept unchanged for the initial 20 min. On the other hand, 4a obtained from cyclohexanone and phenylacetylene was totally stable under the given reaction conditions for 24 h and was recovered unchanged. Use of 100 mol % 3 for the reaction of 21 with 1d in DMSO resulted in a complex mixture after several minutes at room temperature, from which 23% yield of 4-O-benzyl-1-(p-chlorophenyl)-2-butyne-1,4-diol was obtained through very careful chromatographic purification.
16. Aromatic aldehydes and ketones have been reported to undergo side reactions when CsOH was employed: see ref 2.
17. 6 showed very slow deprotonation from 1b at ambient temperature, whereas a similar experiment exhibited very rapid deprotonation from 1a. Although we have no distinctive idea at present about the surprising difference of 1b in reactivity toward 2a and 2j or paraformaldehyde, these interesting observations might suggest that there exists a significant difference in kinetic acidity between 1a and 1b.
18. We should have included results for more systematic experiments using acetylides bearing substituents on the aromatic ring of 1a, which will be done in the near future and reported elsewhere.
19. For the formation of chalcone derivatives from propargylic alcohols of type II (Scheme 3) under the Sonogashira coupling conditions (Takahashi, S.; Kuroyama, Y.; Sonogashira, K.; Hagihara, N. Synthesis 1980, 627), see: Müller, T. J.; Ansorge, M.; Aktah, D. Angew. Chem., Int. Ed. 2000, 39, 1253-1256.
20. For the formation of chalcone derivatives from propargylic alcohols of type II (Scheme 3) under the Sonogashira coupling conditions (Takahashi, S.; Kuroyama, Y.; Sonogashira, K.; Hagihara, N. Synthesis 1980, 627), see: Müller, T. J.; Ansorge, M.; Aktah, D. Angew. Chem., Int. Ed. 2000, 39, 1253-1256.
21. t-BuOK-catalyzed system afforded similar results (unpublished observation). The formation of 6 might be pertinent at least partly to the observed low yields of propargylic alcohols for aromatic aldehydes (entries 6-9 in Table 2).
22. Commercially available resin was used as received. Although the amount and kind of resin might affect the reactivity or the product yield, no effort was made in this context.
23. Physical evidence for the existence of long-lived quaternary ammonium acetylides has not been obtained yet in terms of an NMR probe.