Strategy for the preparation of allenes from α,β-unsaturated and saturated ketones via enol phosphates

Journal of Organic Chemistry

Volumn 61, Issue 18, 1996, Pages 6096-6097

  Brummond, Kay M ^a   Dingess, Elizabeth A ^a   Kent, Joseph L ^a,b  

^a WEST VIRGINIA UNIVERSITY   (United States)

^b Davis and Elkins College   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000227909     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9610265     Document Type: Article

References (24)

1. Schlessinger, R. H.; Bergstrom, C. P. J. Org. Chem. 1995, 60, 16. Sigman, M. S.; Eaton, B. E. J. Org. Chem. 1994, 59, 7488. Jung, M. E.; Zimmerman, C. N.; Lowen, G. T.; Khan, S. I. Tetrahedron Lett. 1993, 34, 4453. Andemichael, Y. W.; Gu, Y. G.; Wang, K. K. J. Org. Chem. 1992, 57, 794.
2. Schlessinger, R. H.; Bergstrom, C. P. J. Org. Chem. 1995, 60, 16. Sigman, M. S.; Eaton, B. E. J. Org. Chem. 1994, 59, 7488. Jung, M. E.; Zimmerman, C. N.; Lowen, G. T.; Khan, S. I. Tetrahedron Lett. 1993, 34, 4453. Andemichael, Y. W.; Gu, Y. G.; Wang, K. K. J. Org. Chem. 1992, 57, 794.
3. Schlessinger, R. H.; Bergstrom, C. P. J. Org. Chem. 1995, 60, 16. Sigman, M. S.; Eaton, B. E. J. Org. Chem. 1994, 59, 7488. Jung, M. E.; Zimmerman, C. N.; Lowen, G. T.; Khan, S. I. Tetrahedron Lett. 1993, 34, 4453. Andemichael, Y. W.; Gu, Y. G.; Wang, K. K. J. Org. Chem. 1992, 57, 794.
4. Schlessinger, R. H.; Bergstrom, C. P. J. Org. Chem. 1995, 60, 16. Sigman, M. S.; Eaton, B. E. J. Org. Chem. 1994, 59, 7488. Jung, M. E.; Zimmerman, C. N.; Lowen, G. T.; Khan, S. I. Tetrahedron Lett. 1993, 34, 4453. Andemichael, Y. W.; Gu, Y. G.; Wang, K. K. J. Org. Chem. 1992, 57, 794.
5. Kent, J. L.; Wan, H.; Brummond, K. M. Tetrahedron Lett. 1995, 36, 2407.
6. Reviews on synthesis and reactions of allenes: Schuster, H. F.; Coppola, G. M. Allenes in Organic Synthesis; Wiley: New York, 1984. Pasto, D. J. Tetrahedron 1984, 40, 2805.
7. Reviews on synthesis and reactions of allenes: Schuster, H. F.; Coppola, G. M. Allenes in Organic Synthesis; Wiley: New York, 1984. Pasto, D. J. Tetrahedron 1984, 40, 2805.
8. Gibbs, R. A.; Bartels, K.; Lee, R. W. K.; Okamura, W. H. J. Am. Chem. Soc. 1989, 111, 3717. Okamura, W. H.; Peter, R.; Reischl, W. J. Am. Chem. Soc. 1985, 107, 1034.
9. Gibbs, R. A.; Bartels, K.; Lee, R. W. K.; Okamura, W. H. J. Am. Chem. Soc. 1989, 111, 3717. Okamura, W. H.; Peter, R.; Reischl, W. J. Am. Chem. Soc. 1985, 107, 1034.
10. For other methods of preparing allenes from ketones see: (a) Satoh, T.; Itoh, N.; Watanabe, S.; Koike, H.; Matsuno, H.; Matsudo, K.; Yamakawa, K. Tetrahedron 1995, 51, 9327. (b) Danheiser, R. L.; Choi, Y. M.; Menichincheri, M.; Stoner, E. J.; J. Org. Chem. 1993, 58, 322. (c) Chan, T. H.; Mychajlowskij, W.; Ong, B. S.; Harpp, D. N. J. Org. Chem. 1978, 43, 1526. (d) Kabalka, G. W.; Newton, R. J.; Chandler, J. H. J. Chem. Soc., Chem. Commun. 1978, 726. (e) Posner, G. H; Tang, P-W; Mallamo, J. P. Tetrahedron Lett. 1978, 19, 3995. (f) Stang, P. J.; Hargrove, R. J. J. Org. Chem. 1975, 40, 657. For an example of the elimination of an enol phosphate flanked by activating groups, see: (g) Craig, J. C.; Moyle, M. J. Chem. Soc. 1963, 3712, 5356.
11. For other methods of preparing allenes from ketones see: (a) Satoh, T.; Itoh, N.; Watanabe, S.; Koike, H.; Matsuno, H.; Matsudo, K.; Yamakawa, K. Tetrahedron 1995, 51, 9327. (b) Danheiser, R. L.; Choi, Y. M.; Menichincheri, M.; Stoner, E. J.; J. Org. Chem. 1993, 58, 322. (c) Chan, T. H.; Mychajlowskij, W.; Ong, B. S.; Harpp, D. N. J. Org. Chem. 1978, 43, 1526. (d) Kabalka, G. W.; Newton, R. J.; Chandler, J. H. J. Chem. Soc., Chem. Commun. 1978, 726. (e) Posner, G. H; Tang, P-W; Mallamo, J. P. Tetrahedron Lett. 1978, 19, 3995. (f) Stang, P. J.; Hargrove, R. J. J. Org. Chem. 1975, 40, 657. For an example of the elimination of an enol phosphate flanked by activating groups, see: (g) Craig, J. C.; Moyle, M. J. Chem. Soc. 1963, 3712, 5356.
12. For other methods of preparing allenes from ketones see: (a) Satoh, T.; Itoh, N.; Watanabe, S.; Koike, H.; Matsuno, H.; Matsudo, K.; Yamakawa, K. Tetrahedron 1995, 51, 9327. (b) Danheiser, R. L.; Choi, Y. M.; Menichincheri, M.; Stoner, E. J.; J. Org. Chem. 1993, 58, 322. (c) Chan, T. H.; Mychajlowskij, W.; Ong, B. S.; Harpp, D. N. J. Org. Chem. 1978, 43, 1526. (d) Kabalka, G. W.; Newton, R. J.; Chandler, J. H. J. Chem. Soc., Chem. Commun. 1978, 726. (e) Posner, G. H; Tang, P-W; Mallamo, J. P. Tetrahedron Lett. 1978, 19, 3995. (f) Stang, P. J.; Hargrove, R. J. J. Org. Chem. 1975, 40, 657. For an example of the elimination of an enol phosphate flanked by activating groups, see: (g) Craig, J. C.; Moyle, M. J. Chem. Soc. 1963, 3712, 5356.
13. For other methods of preparing allenes from ketones see: (a) Satoh, T.; Itoh, N.; Watanabe, S.; Koike, H.; Matsuno, H.; Matsudo, K.; Yamakawa, K. Tetrahedron 1995, 51, 9327. (b) Danheiser, R. L.; Choi, Y. M.; Menichincheri, M.; Stoner, E. J.; J. Org. Chem. 1993, 58, 322. (c) Chan, T. H.; Mychajlowskij, W.; Ong, B. S.; Harpp, D. N. J. Org. Chem. 1978, 43, 1526. (d) Kabalka, G. W.; Newton, R. J.; Chandler, J. H. J. Chem. Soc., Chem. Commun. 1978, 726. (e) Posner, G. H; Tang, P-W; Mallamo, J. P. Tetrahedron Lett. 1978, 19, 3995. (f) Stang, P. J.; Hargrove, R. J. J. Org. Chem. 1975, 40, 657. For an example of the elimination of an enol phosphate flanked by activating groups, see: (g) Craig, J. C.; Moyle, M. J. Chem. Soc. 1963, 3712, 5356.
14. For other methods of preparing allenes from ketones see: (a) Satoh, T.; Itoh, N.; Watanabe, S.; Koike, H.; Matsuno, H.; Matsudo, K.; Yamakawa, K. Tetrahedron 1995, 51, 9327. (b) Danheiser, R. L.; Choi, Y. M.; Menichincheri, M.; Stoner, E. J.; J. Org. Chem. 1993, 58, 322. (c) Chan, T. H.; Mychajlowskij, W.; Ong, B. S.; Harpp, D. N. J. Org. Chem. 1978, 43, 1526. (d) Kabalka, G. W.; Newton, R. J.; Chandler, J. H. J. Chem. Soc., Chem. Commun. 1978, 726. (e) Posner, G. H; Tang, P-W; Mallamo, J. P. Tetrahedron Lett. 1978, 19, 3995. (f) Stang, P. J.; Hargrove, R. J. J. Org. Chem. 1975, 40, 657. For an example of the elimination of an enol phosphate flanked by activating groups, see: (g) Craig, J. C.; Moyle, M. J. Chem. Soc. 1963, 3712, 5356.
15. For other methods of preparing allenes from ketones see: (a) Satoh, T.; Itoh, N.; Watanabe, S.; Koike, H.; Matsuno, H.; Matsudo, K.; Yamakawa, K. Tetrahedron 1995, 51, 9327. (b) Danheiser, R. L.; Choi, Y. M.; Menichincheri, M.; Stoner, E. J.; J. Org. Chem. 1993, 58, 322. (c) Chan, T. H.; Mychajlowskij, W.; Ong, B. S.; Harpp, D. N. J. Org. Chem. 1978, 43, 1526. (d) Kabalka, G. W.; Newton, R. J.; Chandler, J. H. J. Chem. Soc., Chem. Commun. 1978, 726. (e) Posner, G. H; Tang, P-W; Mallamo, J. P. Tetrahedron Lett. 1978, 19, 3995. (f) Stang, P. J.; Hargrove, R. J. J. Org. Chem. 1975, 40, 657. For an example of the elimination of an enol phosphate flanked by activating groups, see: (g) Craig, J. C.; Moyle, M. J. Chem. Soc. 1963, 3712, 5356.
16. For other methods of preparing allenes from ketones see: (a) Satoh, T.; Itoh, N.; Watanabe, S.; Koike, H.; Matsuno, H.; Matsudo, K.; Yamakawa, K. Tetrahedron 1995, 51, 9327. (b) Danheiser, R. L.; Choi, Y. M.; Menichincheri, M.; Stoner, E. J.; J. Org. Chem. 1993, 58, 322. (c) Chan, T. H.; Mychajlowskij, W.; Ong, B. S.; Harpp, D. N. J. Org. Chem. 1978, 43, 1526. (d) Kabalka, G. W.; Newton, R. J.; Chandler, J. H. J. Chem. Soc., Chem. Commun. 1978, 726. (e) Posner, G. H; Tang, P-W; Mallamo, J. P. Tetrahedron Lett. 1978, 19, 3995. (f) Stang, P. J.; Hargrove, R. J. J. Org. Chem. 1975, 40, 657. For an example of the elimination of an enol phosphate flanked by activating groups, see: (g) Craig, J. C.; Moyle, M. J. Chem. Soc. 1963, 3712, 5356.
17. Negishi, E.-I.; King, A. O.; Klima, W. L. J. Org. Chem. 1980, 45, 2526. Negishi, E.-I.; King, A. O.; Tour, J. M. Org. Synth. 1985, 64, 44.
18. Negishi, E.-I.; King, A. O.; Klima, W. L. J. Org. Chem. 1980, 45, 2526. Negishi, E.-I.; King, A. O.; Tour, J. M. Org. Synth. 1985, 64, 44.
19. Naso, F.; Ronzini, L. J. Chem. Soc., Perkin Trans. 1 1974, 340.
20. Calogeropoulou, T.; Hammond, G. B.; Wiemer, D. F. J. Org. Chem. 1987, 52, 4185.
21. HPLC peak identity was determined by coinjection of 2- and 3-octyne with the crude product mixture. The response factor of the RI detector to 2,3-octadiene and 2-octyne was determined to be 1.11.
22. A control experiment was carried out where an allene was subjected to the conditions employed for the elimination step and isomerization of the allene to acetylene occurred at room temperature.
23. Raquette, L. A.; Pierre, F.; Cottrell, C. E. J. Am. Chem. Soc. 1987, 109, 5731.
24. 4. The solvent was removed in vacuo to afford a yellow oil. (If this elimination reaction is stirred at -78°C for only 16 h, 1-phenyl-3,4-octadiene is afforded in 63% yield and the HPLC trace of the crude product shows a 97:3 ratio of allene to alkyne.) Purification by flash chromatography on silica gel (eluting with pentane) furnished a 73% yield 1-phenyl3,4-octadiene and 7% combined yield of 1-phenyl-3-octyne and 1-phenyl-4-octyne as colorless oils. The HPLC trace of the crude product shows a 90:10 ratio of allene to alkyne. The selectivity was determined by the HPLC method using a silica column with hexanes as the eluent.