Ambident Reactivity of Medium-Ring Cycloalkane-1,3-dione Enolates

Journal of Organic Chemistry

Volumn 63, Issue 4, 1998, Pages 1098-1101

  Thompson, Glenn S ^a   Hirsch, Jerry A ^a  

^a SETON HALL UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000251511     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo971515k     Document Type: Article

References (32)

1. Taken from: Thompson, G. S. Ph.D. Dissertation, Seton Hall University, 1995.
2. House, H. O. Modern Synthetic Reactions, 2nd ed.; W. A. Benjamin, Inc.: Menlo Park, CA, 1972; Chapter 9.
3. Carey, F. A.; Sundberg, R. J. Advanced Organic Chemistry, 2nd ed.; Plenum Press: New York, 1983; Part B, Chapter 1.7.
4. Eskola, P.; Hirsch, J. A. J. Org. Chem. 1997, 62, 5732 and previous papers in the series.
5. Ito, Y.; Fujii, S.; Nakatsuka, M.; Kawamoto, F.; Saegusa, T. Org. Synth. 1979, 59, 113. Ito, Y.; Fujii, S.; Saegusa, T. J. Org. Chem. 1976, 41, 2073.
6. Ito, Y.; Fujii, S.; Nakatsuka, M.; Kawamoto, F.; Saegusa, T. Org. Synth. 1979, 59, 113. Ito, Y.; Fujii, S.; Saegusa, T. J. Org. Chem. 1976, 41, 2073.
7. Pirrung, M. C.; Webster, N. J. G. J. Org. Chem. 1987, 52, 3606.
8. Other syntheses of 3. n = 3: (a) Maclean, I.; Sneeden, R. P. A. Tetrahedron 1965, 21, 31. (b) Eistert, B.; Haupter, F.; Schank, K. Justus Liebig Ann. Chem. 1963, 665, 55. (c) Bhushan, V.; Chandrasekaran, S. Synth. Commun. 1984, 14, 339. n = 3, 4, and 8: (d) Suzuki, M.; Watanabe, A.; Noyori, R. J. Am. Chem. Soc. 1980, 102, 2095. n = 3-5: (e) Nishiguchi, I.; Hirashima, T.; Shono, T.; Sasaki, M. Chem. Lett. 1981, 551. n = 4-8: (f) Schank, K.; Eistert, B.; Felzmann, J. H. Chem. Ber. 1966, 99, 1414. Eistert, B.; Schank, K. Tetrahedron Lett. 1964, 8, 429. n = 6 and 7: (g) Beccalli, E. G.; Majori, L.; Marchesini, A. J. Org. Chem. 1981, 46, 222. n = 7-11 and 13: (h) Hunig, S.; Hoch, H. Tetrahedron Lett. 1966, 42, 5215; Liebigs Ann. Chem. 1968, 716, 68. (i) Kirrmann, A.; Wakselman, C. Bull. Soc. Chim. Fr. 1967, 10, 3772. n = 11: Reference 5. n = 3-5 with 2-methyl substituent: (j) Brooks, D. W.; Mazdiyasni, H.; Sallay, P. J. Org. Chem. 1985, 50, 3411.
9. Other syntheses of 3. n = 3: (a) Maclean, I.; Sneeden, R. P. A. Tetrahedron 1965, 21, 31. (b) Eistert, B.; Haupter, F.; Schank, K. Justus Liebig Ann. Chem. 1963, 665, 55. (c) Bhushan, V.; Chandrasekaran, S. Synth. Commun. 1984, 14, 339. n = 3, 4, and 8: (d) Suzuki, M.; Watanabe, A.; Noyori, R. J. Am. Chem. Soc. 1980, 102, 2095. n = 3-5: (e) Nishiguchi, I.; Hirashima, T.; Shono, T.; Sasaki, M. Chem. Lett. 1981, 551. n = 4-8: (f) Schank, K.; Eistert, B.; Felzmann, J. H. Chem. Ber. 1966, 99, 1414. Eistert, B.; Schank, K. Tetrahedron Lett. 1964, 8, 429. n = 6 and 7: (g) Beccalli, E. G.; Majori, L.; Marchesini, A. J. Org. Chem. 1981, 46, 222. n = 7-11 and 13: (h) Hunig, S.; Hoch, H. Tetrahedron Lett. 1966, 42, 5215; Liebigs Ann. Chem. 1968, 716, 68. (i) Kirrmann, A.; Wakselman, C. Bull. Soc. Chim. Fr. 1967, 10, 3772. n = 11: Reference 5. n = 3-5 with 2-methyl substituent: (j) Brooks, D. W.; Mazdiyasni, H.; Sallay, P. J. Org. Chem. 1985, 50, 3411.
10. Other syntheses of 3. n = 3: (a) Maclean, I.; Sneeden, R. P. A. Tetrahedron 1965, 21, 31. (b) Eistert, B.; Haupter, F.; Schank, K. Justus Liebig Ann. Chem. 1963, 665, 55. (c) Bhushan, V.; Chandrasekaran, S. Synth. Commun. 1984, 14, 339. n = 3, 4, and 8: (d) Suzuki, M.; Watanabe, A.; Noyori, R. J. Am. Chem. Soc. 1980, 102, 2095. n = 3-5: (e) Nishiguchi, I.; Hirashima, T.; Shono, T.; Sasaki, M. Chem. Lett. 1981, 551. n = 4-8: (f) Schank, K.; Eistert, B.; Felzmann, J. H. Chem. Ber. 1966, 99, 1414. Eistert, B.; Schank, K. Tetrahedron Lett. 1964, 8, 429. n = 6 and 7: (g) Beccalli, E. G.; Majori, L.; Marchesini, A. J. Org. Chem. 1981, 46, 222. n = 7-11 and 13: (h) Hunig, S.; Hoch, H. Tetrahedron Lett. 1966, 42, 5215; Liebigs Ann. Chem. 1968, 716, 68. (i) Kirrmann, A.; Wakselman, C. Bull. Soc. Chim. Fr. 1967, 10, 3772. n = 11: Reference 5. n = 3-5 with 2-methyl substituent: (j) Brooks, D. W.; Mazdiyasni, H.; Sallay, P. J. Org. Chem. 1985, 50, 3411.
11. Other syntheses of 3. n = 3: (a) Maclean, I.; Sneeden, R. P. A. Tetrahedron 1965, 21, 31. (b) Eistert, B.; Haupter, F.; Schank, K. Justus Liebig Ann. Chem. 1963, 665, 55. (c) Bhushan, V.; Chandrasekaran, S. Synth. Commun. 1984, 14, 339. n = 3, 4, and 8: (d) Suzuki, M.; Watanabe, A.; Noyori, R. J. Am. Chem. Soc. 1980, 102, 2095. n = 3-5: (e) Nishiguchi, I.; Hirashima, T.; Shono, T.; Sasaki, M. Chem. Lett. 1981, 551. n = 4-8: (f) Schank, K.; Eistert, B.; Felzmann, J. H. Chem. Ber. 1966, 99, 1414. Eistert, B.; Schank, K. Tetrahedron Lett. 1964, 8, 429. n = 6 and 7: (g) Beccalli, E. G.; Majori, L.; Marchesini, A. J. Org. Chem. 1981, 46, 222. n = 7-11 and 13: (h) Hunig, S.; Hoch, H. Tetrahedron Lett. 1966, 42, 5215; Liebigs Ann. Chem. 1968, 716, 68. (i) Kirrmann, A.; Wakselman, C. Bull. Soc. Chim. Fr. 1967, 10, 3772. n = 11: Reference 5. n = 3-5 with 2-methyl substituent: (j) Brooks, D. W.; Mazdiyasni, H.; Sallay, P. J. Org. Chem. 1985, 50, 3411.
12. Other syntheses of 3. n = 3: (a) Maclean, I.; Sneeden, R. P. A. Tetrahedron 1965, 21, 31. (b) Eistert, B.; Haupter, F.; Schank, K. Justus Liebig Ann. Chem. 1963, 665, 55. (c) Bhushan, V.; Chandrasekaran, S. Synth. Commun. 1984, 14, 339. n = 3, 4, and 8: (d) Suzuki, M.; Watanabe, A.; Noyori, R. J. Am. Chem. Soc. 1980, 102, 2095. n = 3-5: (e) Nishiguchi, I.; Hirashima, T.; Shono, T.; Sasaki, M. Chem. Lett. 1981, 551. n = 4-8: (f) Schank, K.; Eistert, B.; Felzmann, J. H. Chem. Ber. 1966, 99, 1414. Eistert, B.; Schank, K. Tetrahedron Lett. 1964, 8, 429. n = 6 and 7: (g) Beccalli, E. G.; Majori, L.; Marchesini, A. J. Org. Chem. 1981, 46, 222. n = 7-11 and 13: (h) Hunig, S.; Hoch, H. Tetrahedron Lett. 1966, 42, 5215; Liebigs Ann. Chem. 1968, 716, 68. (i) Kirrmann, A.; Wakselman, C. Bull. Soc. Chim. Fr. 1967, 10, 3772. n = 11: Reference 5. n = 3-5 with 2-methyl substituent: (j) Brooks, D. W.; Mazdiyasni, H.; Sallay, P. J. Org. Chem. 1985, 50, 3411.
13. Other syntheses of 3. n = 3: (a) Maclean, I.; Sneeden, R. P. A. Tetrahedron 1965, 21, 31. (b) Eistert, B.; Haupter, F.; Schank, K. Justus Liebig Ann. Chem. 1963, 665, 55. (c) Bhushan, V.; Chandrasekaran, S. Synth. Commun. 1984, 14, 339. n = 3, 4, and 8: (d) Suzuki, M.; Watanabe, A.; Noyori, R. J. Am. Chem. Soc. 1980, 102, 2095. n = 3-5: (e) Nishiguchi, I.; Hirashima, T.; Shono, T.; Sasaki, M. Chem. Lett. 1981, 551. n = 4-8: (f) Schank, K.; Eistert, B.; Felzmann, J. H. Chem. Ber. 1966, 99, 1414. Eistert, B.; Schank, K. Tetrahedron Lett. 1964, 8, 429. n = 6 and 7: (g) Beccalli, E. G.; Majori, L.; Marchesini, A. J. Org. Chem. 1981, 46, 222. n = 7-11 and 13: (h) Hunig, S.; Hoch, H. Tetrahedron Lett. 1966, 42, 5215; Liebigs Ann. Chem. 1968, 716, 68. (i) Kirrmann, A.; Wakselman, C. Bull. Soc. Chim. Fr. 1967, 10, 3772. n = 11: Reference 5. n = 3-5 with 2-methyl substituent: (j) Brooks, D. W.; Mazdiyasni, H.; Sallay, P. J. Org. Chem. 1985, 50, 3411.
14. Other syntheses of 3. n = 3: (a) Maclean, I.; Sneeden, R. P. A. Tetrahedron 1965, 21, 31. (b) Eistert, B.; Haupter, F.; Schank, K. Justus Liebig Ann. Chem. 1963, 665, 55. (c) Bhushan, V.; Chandrasekaran, S. Synth. Commun. 1984, 14, 339. n = 3, 4, and 8: (d) Suzuki, M.; Watanabe, A.; Noyori, R. J. Am. Chem. Soc. 1980, 102, 2095. n = 3-5: (e) Nishiguchi, I.; Hirashima, T.; Shono, T.; Sasaki, M. Chem. Lett. 1981, 551. n = 4-8: (f) Schank, K.; Eistert, B.; Felzmann, J. H. Chem. Ber. 1966, 99, 1414. Eistert, B.; Schank, K. Tetrahedron Lett. 1964, 8, 429. n = 6 and 7: (g) Beccalli, E. G.; Majori, L.; Marchesini, A. J. Org. Chem. 1981, 46, 222. n = 7-11 and 13: (h) Hunig, S.; Hoch, H. Tetrahedron Lett. 1966, 42, 5215; Liebigs Ann. Chem. 1968, 716, 68. (i) Kirrmann, A.; Wakselman, C. Bull. Soc. Chim. Fr. 1967, 10, 3772. n = 11: Reference 5. n = 3-5 with 2-methyl substituent: (j) Brooks, D. W.; Mazdiyasni, H.; Sallay, P. J. Org. Chem. 1985, 50, 3411.
15. Other syntheses of 3. n = 3: (a) Maclean, I.; Sneeden, R. P. A. Tetrahedron 1965, 21, 31. (b) Eistert, B.; Haupter, F.; Schank, K. Justus Liebig Ann. Chem. 1963, 665, 55. (c) Bhushan, V.; Chandrasekaran, S. Synth. Commun. 1984, 14, 339. n = 3, 4, and 8: (d) Suzuki, M.; Watanabe, A.; Noyori, R. J. Am. Chem. Soc. 1980, 102, 2095. n = 3-5: (e) Nishiguchi, I.; Hirashima, T.; Shono, T.; Sasaki, M. Chem. Lett. 1981, 551. n = 4-8: (f) Schank, K.; Eistert, B.; Felzmann, J. H. Chem. Ber. 1966, 99, 1414. Eistert, B.; Schank, K. Tetrahedron Lett. 1964, 8, 429. n = 6 and 7: (g) Beccalli, E. G.; Majori, L.; Marchesini, A. J. Org. Chem. 1981, 46, 222. n = 7-11 and 13: (h) Hunig, S.; Hoch, H. Tetrahedron Lett. 1966, 42, 5215; Liebigs Ann. Chem. 1968, 716, 68. (i) Kirrmann, A.; Wakselman, C. Bull. Soc. Chim. Fr. 1967, 10, 3772. n = 11: Reference 5. n = 3-5 with 2-methyl substituent: (j) Brooks, D. W.; Mazdiyasni, H.; Sallay, P. J. Org. Chem. 1985, 50, 3411.
16. Other syntheses of 3. n = 3: (a) Maclean, I.; Sneeden, R. P. A. Tetrahedron 1965, 21, 31. (b) Eistert, B.; Haupter, F.; Schank, K. Justus Liebig Ann. Chem. 1963, 665, 55. (c) Bhushan, V.; Chandrasekaran, S. Synth. Commun. 1984, 14, 339. n = 3, 4, and 8: (d) Suzuki, M.; Watanabe, A.; Noyori, R. J. Am. Chem. Soc. 1980, 102, 2095. n = 3-5: (e) Nishiguchi, I.; Hirashima, T.; Shono, T.; Sasaki, M. Chem. Lett. 1981, 551. n = 4-8: (f) Schank, K.; Eistert, B.; Felzmann, J. H. Chem. Ber. 1966, 99, 1414. Eistert, B.; Schank, K. Tetrahedron Lett. 1964, 8, 429. n = 6 and 7: (g) Beccalli, E. G.; Majori, L.; Marchesini, A. J. Org. Chem. 1981, 46, 222. n = 7-11 and 13: (h) Hunig, S.; Hoch, H. Tetrahedron Lett. 1966, 42, 5215; Liebigs Ann. Chem. 1968, 716, 68. (i) Kirrmann, A.; Wakselman, C. Bull. Soc. Chim. Fr. 1967, 10, 3772. n = 11: Reference 5. n = 3-5 with 2-methyl substituent: (j) Brooks, D. W.; Mazdiyasni, H.; Sallay, P. J. Org. Chem. 1985, 50, 3411.
17. Other syntheses of 3. n = 3: (a) Maclean, I.; Sneeden, R. P. A. Tetrahedron 1965, 21, 31. (b) Eistert, B.; Haupter, F.; Schank, K. Justus Liebig Ann. Chem. 1963, 665, 55. (c) Bhushan, V.; Chandrasekaran, S. Synth. Commun. 1984, 14, 339. n = 3, 4, and 8: (d) Suzuki, M.; Watanabe, A.; Noyori, R. J. Am. Chem. Soc. 1980, 102, 2095. n = 3-5: (e) Nishiguchi, I.; Hirashima, T.; Shono, T.; Sasaki, M. Chem. Lett. 1981, 551. n = 4-8: (f) Schank, K.; Eistert, B.; Felzmann, J. H. Chem. Ber. 1966, 99, 1414. Eistert, B.; Schank, K. Tetrahedron Lett. 1964, 8, 429. n = 6 and 7: (g) Beccalli, E. G.; Majori, L.; Marchesini, A. J. Org. Chem. 1981, 46, 222. n = 7-11 and 13: (h) Hunig, S.; Hoch, H. Tetrahedron Lett. 1966, 42, 5215; Liebigs Ann. Chem. 1968, 716, 68. (i) Kirrmann, A.; Wakselman, C. Bull. Soc. Chim. Fr. 1967, 10, 3772. n = 11: Reference 5. n = 3-5 with 2-methyl substituent: (j) Brooks, D. W.; Mazdiyasni, H.; Sallay, P. J. Org. Chem. 1985, 50, 3411.
18. Other syntheses of 3. n = 3: (a) Maclean, I.; Sneeden, R. P. A. Tetrahedron 1965, 21, 31. (b) Eistert, B.; Haupter, F.; Schank, K. Justus Liebig Ann. Chem. 1963, 665, 55. (c) Bhushan, V.; Chandrasekaran, S. Synth. Commun. 1984, 14, 339. n = 3, 4, and 8: (d) Suzuki, M.; Watanabe, A.; Noyori, R. J. Am. Chem. Soc. 1980, 102, 2095. n = 3-5: (e) Nishiguchi, I.; Hirashima, T.; Shono, T.; Sasaki, M. Chem. Lett. 1981, 551. n = 4-8: (f) Schank, K.; Eistert, B.; Felzmann, J. H. Chem. Ber. 1966, 99, 1414. Eistert, B.; Schank, K. Tetrahedron Lett. 1964, 8, 429. n = 6 and 7: (g) Beccalli, E. G.; Majori, L.; Marchesini, A. J. Org. Chem. 1981, 46, 222. n = 7-11 and 13: (h) Hunig, S.; Hoch, H. Tetrahedron Lett. 1966, 42, 5215; Liebigs Ann. Chem. 1968, 716, 68. (i) Kirrmann, A.; Wakselman, C. Bull. Soc. Chim. Fr. 1967, 10, 3772. n = 11: Reference 5. n = 3-5 with 2-methyl substituent: (j) Brooks, D. W.; Mazdiyasni, H.; Sallay, P. J. Org. Chem. 1985, 50, 3411.
19. Other syntheses of 3. n = 3: (a) Maclean, I.; Sneeden, R. P. A. Tetrahedron 1965, 21, 31. (b) Eistert, B.; Haupter, F.; Schank, K. Justus Liebig Ann. Chem. 1963, 665, 55. (c) Bhushan, V.; Chandrasekaran, S. Synth. Commun. 1984, 14, 339. n = 3, 4, and 8: (d) Suzuki, M.; Watanabe, A.; Noyori, R. J. Am. Chem. Soc. 1980, 102, 2095. n = 3-5: (e) Nishiguchi, I.; Hirashima, T.; Shono, T.; Sasaki, M. Chem. Lett. 1981, 551. n = 4-8: (f) Schank, K.; Eistert, B.; Felzmann, J. H. Chem. Ber. 1966, 99, 1414. Eistert, B.; Schank, K. Tetrahedron Lett. 1964, 8, 429. n = 6 and 7: (g) Beccalli, E. G.; Majori, L.; Marchesini, A. J. Org. Chem. 1981, 46, 222. n = 7-11 and 13: (h) Hunig, S.; Hoch, H. Tetrahedron Lett. 1966, 42, 5215; Liebigs Ann. Chem. 1968, 716, 68. (i) Kirrmann, A.; Wakselman, C. Bull. Soc. Chim. Fr. 1967, 10, 3772. n = 11: Reference 5. n = 3-5 with 2-methyl substituent: (j) Brooks, D. W.; Mazdiyasni, H.; Sallay, P. J. Org. Chem. 1985, 50, 3411.
20. Sraga, J.; Hrnciar, P. Chem. Zvesti 1981, 35, 119.
21. O/C ratios are the amount of 2-alkoxyenone (1 + 2) plus any 1,3-dialkoxydiene (9) relative to the total amount of 2-alkyl (6), 2,2-dialkyl (7), 2,2,4-trialkyl 1,3-dione (10), and 2-alkyl-3-alkoxy enone (8).
22. Ho, T. L. Hard and Soft Acids and Bases Principle in Organic Chemistry; Academic Press: New York, 1977.
23. Rhoads, S. J.; Hasbrouck, R. W. Tetrahedron 1966, 22, 3557. Rhoads, S. J.; Decora, A. W. Tetrahedron 1963, 19, 1645. Rhoads, S. J.; Holder, R. W. Tetrahedron 1969, 25, 5443.
24. Rhoads, S. J.; Hasbrouck, R. W. Tetrahedron 1966, 22, 3557. Rhoads, S. J.; Decora, A. W. Tetrahedron 1963, 19, 1645. Rhoads, S. J.; Holder, R. W. Tetrahedron 1969, 25, 5443.
25. Rhoads, S. J.; Hasbrouck, R. W. Tetrahedron 1966, 22, 3557. Rhoads, S. J.; Decora, A. W. Tetrahedron 1963, 19, 1645. Rhoads, S. J.; Holder, R. W. Tetrahedron 1969, 25, 5443.
26. Heap, N.; Whitham, G. H. J. Chem. Soc. B 1966, 164. Whitham, G. H.; Zaidlewicz, M. J. Chem. Soc., Perkin Trans. 1 1972, 1509.
27. Heap, N.; Whitham, G. H. J. Chem. Soc. B 1966, 164. Whitham, G. H.; Zaidlewicz, M. J. Chem. Soc., Perkin Trans. 1 1972, 1509.
28. Ruhlmann, K. Synthesis 1971, 236.
29. Fieser, L. F.; Fieser, M. Reagents for Organic Synthesis; John Wiley and Sons: New York, 1967; pp 1022-1023. preparation of a fine and clean Na sand is critical.
30. Lewicka-Piekut, S.; Okamura, W. H. Synth. Commun. 1980, 10, 415.
31. Schrapler, U.; Ruhlmann, K. Chem. Ber. 1964, 97, 1383.
32. Reference 14, p 1180.