Synthesis of unsymmetrically substituted 1,3-butadiynes and 1,3,5-hexatriynes via alkylidene carbenoid rearrangements

Journal of Organic Chemistry

Volumn 68, Issue 4, 2003, Pages 1339-1347

  Shi Shun, Annabelle L K ^a   Chernick, Erin T ^a   Eisler, Sara ^a   Tykwinski, Rik R ^a  

^a UNIVERSITY OF ALBERTA   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

FRITSCH-BUTTENBERG-WIECHERR REARRANGEMENT;

CARBOXYLIC ACIDS; CATALYSIS; COPPER; PALLADIUM; SYNTHESIS (CHEMICAL);

ALDEHYDES;

1,3 BUTADIENE; 1,3 BUTADIYNE DERIVATIVE; 1,3,5 HEXATRIYNE DERIVATIVE; ALDEHYDE DERIVATIVE; ALKYL GROUP; CARBENOID; CARBOXYLIC ACID; COPPER; PALLADIUM; POLYENE; UNCLASSIFIED DRUG;

ARTICLE; CATALYSIS; CHEMICAL REACTION; CHEMICAL STRUCTURE; REACTION ANALYSIS; STRUCTURE ANALYSIS; SYNTHESIS;

EID: 0037458895     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo026481h     Document Type: Article

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79. For other examples of unsymmetrical diyne syntheses, see: (a) Alami, M.; Ferri, F. Tetrahedron Lett. 1996, 37, 2763-2766. (b) Kwon, J. H.; Lee, S. T.; Shim, S. C.; Hoshino, M. J. Org. Chem. 1994, 59, 1108-1114. (c) Aitken, R. A.; Seth, S. J. Chem. Soc., Perkin Trans. 1 1994, 2461-2466. (d) Blanco, L.; Helson, H. E.; Hirthammer, M.; Mestdagh, H.; Spyroudis, S.; Vollhardt, K. P. C. Angew. Chem., Int. Ed. Engl. 1987, 26, 1246-1247. (e) Ziegler, C. B., Jr.; Harris, S. M.; Baldwin, J. E. J. Org. Chem. 1987, 52, 443-446. (f) Fritzsche, U.; Hünig, S. Tetrahedron Lett. 1972, 4831-4834. (g) Lu, W.; Zheng, G.; Aisa, H. A.; Cai, J. Tetrahedron Lett. 1998, 39, 9521-9522. (h) Zheng, G.; Lu, W.; Cai, J. J. Nat. Prod. 1999, 62, 626-628. (i) Nishihara, Y.; Ikegashira, K.; Hirabayashi, K.; Ando, J.; Mori, A.; Hiyama, T. J. Org. Chem. 2000, 65, 1780-1787. (j) Nishihara, Y.; Ikegashira, K.; Mori, A.; Hiyama, T. Tetrahedron Lett. 1998, 39, 4075-4078. For another example of unsymmetrical triyne synthesis, see: Gardner, J. N.; Jones, E. R. H.; Leeming, P. R.; Stephenson, J. S. J. Chem. Soc. 1960, 691-697.
80. For other examples of unsymmetrical diyne syntheses, see: (a) Alami, M.; Ferri, F. Tetrahedron Lett. 1996, 37, 2763-2766. (b) Kwon, J. H.; Lee, S. T.; Shim, S. C.; Hoshino, M. J. Org. Chem. 1994, 59, 1108-1114. (c) Aitken, R. A.; Seth, S. J. Chem. Soc., Perkin Trans. 1 1994, 2461-2466. (d) Blanco, L.; Helson, H. E.; Hirthammer, M.; Mestdagh, H.; Spyroudis, S.; Vollhardt, K. P. C. Angew. Chem., Int. Ed. Engl. 1987, 26, 1246-1247. (e) Ziegler, C. B., Jr.; Harris, S. M.; Baldwin, J. E. J. Org. Chem. 1987, 52, 443-446. (f) Fritzsche, U.; Hünig, S. Tetrahedron Lett. 1972, 4831-4834. (g) Lu, W.; Zheng, G.; Aisa, H. A.; Cai, J. Tetrahedron Lett. 1998, 39, 9521-9522. (h) Zheng, G.; Lu, W.; Cai, J. J. Nat. Prod. 1999, 62, 626-628. (i) Nishihara, Y.; Ikegashira, K.; Hirabayashi, K.; Ando, J.; Mori, A.; Hiyama, T. J. Org. Chem. 2000, 65, 1780-1787. (j) Nishihara, Y.; Ikegashira, K.; Mori, A.; Hiyama, T. Tetrahedron Lett. 1998, 39, 4075-4078. For another example of unsymmetrical triyne synthesis, see: Gardner, J. N.; Jones, E. R. H.; Leeming, P. R.; Stephenson, J. S. J. Chem. Soc. 1960, 691-697.
81. For other examples of unsymmetrical diyne syntheses, see: (a) Alami, M.; Ferri, F. Tetrahedron Lett. 1996, 37, 2763-2766. (b) Kwon, J. H.; Lee, S. T.; Shim, S. C.; Hoshino, M. J. Org. Chem. 1994, 59, 1108-1114. (c) Aitken, R. A.; Seth, S. J. Chem. Soc., Perkin Trans. 1 1994, 2461-2466. (d) Blanco, L.; Helson, H. E.; Hirthammer, M.; Mestdagh, H.; Spyroudis, S.; Vollhardt, K. P. C. Angew. Chem., Int. Ed. Engl. 1987, 26, 1246-1247. (e) Ziegler, C. B., Jr.; Harris, S. M.; Baldwin, J. E. J. Org. Chem. 1987, 52, 443-446. (f) Fritzsche, U.; Hünig, S. Tetrahedron Lett. 1972, 4831-4834. (g) Lu, W.; Zheng, G.; Aisa, H. A.; Cai, J. Tetrahedron Lett. 1998, 39, 9521-9522. (h) Zheng, G.; Lu, W.; Cai, J. J. Nat. Prod. 1999, 62, 626-628. (i) Nishihara, Y.; Ikegashira, K.; Hirabayashi, K.; Ando, J.; Mori, A.; Hiyama, T. J. Org. Chem. 2000, 65, 1780-1787. (j) Nishihara, Y.; Ikegashira, K.; Mori, A.; Hiyama, T. Tetrahedron Lett. 1998, 39, 4075-4078. For another example of unsymmetrical triyne synthesis, see: Gardner, J. N.; Jones, E. R. H.; Leeming, P. R.; Stephenson, J. S. J. Chem. Soc. 1960, 691-697.
82. For other examples of unsymmetrical diyne syntheses, see: (a) Alami, M.; Ferri, F. Tetrahedron Lett. 1996, 37, 2763-2766. (b) Kwon, J. H.; Lee, S. T.; Shim, S. C.; Hoshino, M. J. Org. Chem. 1994, 59, 1108-1114. (c) Aitken, R. A.; Seth, S. J. Chem. Soc., Perkin Trans. 1 1994, 2461-2466. (d) Blanco, L.; Helson, H. E.; Hirthammer, M.; Mestdagh, H.; Spyroudis, S.; Vollhardt, K. P. C. Angew. Chem., Int. Ed. Engl. 1987, 26, 1246-1247. (e) Ziegler, C. B., Jr.; Harris, S. M.; Baldwin, J. E. J. Org. Chem. 1987, 52, 443-446. (f) Fritzsche, U.; Hünig, S. Tetrahedron Lett. 1972, 4831-4834. (g) Lu, W.; Zheng, G.; Aisa, H. A.; Cai, J. Tetrahedron Lett. 1998, 39, 9521-9522. (h) Zheng, G.; Lu, W.; Cai, J. J. Nat. Prod. 1999, 62, 626-628. (i) Nishihara, Y.; Ikegashira, K.; Hirabayashi, K.; Ando, J.; Mori, A.; Hiyama, T. J. Org. Chem. 2000, 65, 1780-1787. (j) Nishihara, Y.; Ikegashira, K.; Mori, A.; Hiyama, T. Tetrahedron Lett. 1998, 39, 4075-4078. For another example of unsymmetrical triyne synthesis, see: Gardner, J. N.; Jones, E. R. H.; Leeming, P. R.; Stephenson, J. S. J. Chem. Soc. 1960, 691-697.
83. For other examples of unsymmetrical diyne syntheses, see: (a) Alami, M.; Ferri, F. Tetrahedron Lett. 1996, 37, 2763-2766. (b) Kwon, J. H.; Lee, S. T.; Shim, S. C.; Hoshino, M. J. Org. Chem. 1994, 59, 1108-1114. (c) Aitken, R. A.; Seth, S. J. Chem. Soc., Perkin Trans. 1 1994, 2461-2466. (d) Blanco, L.; Helson, H. E.; Hirthammer, M.; Mestdagh, H.; Spyroudis, S.; Vollhardt, K. P. C. Angew. Chem., Int. Ed. Engl. 1987, 26, 1246-1247. (e) Ziegler, C. B., Jr.; Harris, S. M.; Baldwin, J. E. J. Org. Chem. 1987, 52, 443-446. (f) Fritzsche, U.; Hünig, S. Tetrahedron Lett. 1972, 4831-4834. (g) Lu, W.; Zheng, G.; Aisa, H. A.; Cai, J. Tetrahedron Lett. 1998, 39, 9521-9522. (h) Zheng, G.; Lu, W.; Cai, J. J. Nat. Prod. 1999, 62, 626-628. (i) Nishihara, Y.; Ikegashira, K.; Hirabayashi, K.; Ando, J.; Mori, A.; Hiyama, T. J. Org. Chem. 2000, 65, 1780-1787. (j) Nishihara, Y.; Ikegashira, K.; Mori, A.; Hiyama, T. Tetrahedron Lett. 1998, 39, 4075-4078. For another example of unsymmetrical triyne synthesis, see: Gardner, J. N.; Jones, E. R. H.; Leeming, P. R.; Stephenson, J. S. J. Chem. Soc. 1960, 691-697.
84. For other examples of unsymmetrical diyne syntheses, see: (a) Alami, M.; Ferri, F. Tetrahedron Lett. 1996, 37, 2763-2766. (b) Kwon, J. H.; Lee, S. T.; Shim, S. C.; Hoshino, M. J. Org. Chem. 1994, 59, 1108-1114. (c) Aitken, R. A.; Seth, S. J. Chem. Soc., Perkin Trans. 1 1994, 2461-2466. (d) Blanco, L.; Helson, H. E.; Hirthammer, M.; Mestdagh, H.; Spyroudis, S.; Vollhardt, K. P. C. Angew. Chem., Int. Ed. Engl. 1987, 26, 1246-1247. (e) Ziegler, C. B., Jr.; Harris, S. M.; Baldwin, J. E. J. Org. Chem. 1987, 52, 443-446. (f) Fritzsche, U.; Hünig, S. Tetrahedron Lett. 1972, 4831-4834. (g) Lu, W.; Zheng, G.; Aisa, H. A.; Cai, J. Tetrahedron Lett. 1998, 39, 9521-9522. (h) Zheng, G.; Lu, W.; Cai, J. J. Nat. Prod. 1999, 62, 626-628. (i) Nishihara, Y.; Ikegashira, K.; Hirabayashi, K.; Ando, J.; Mori, A.; Hiyama, T. J. Org. Chem. 2000, 65, 1780-1787. (j) Nishihara, Y.; Ikegashira, K.; Mori, A.; Hiyama, T. Tetrahedron Lett. 1998, 39, 4075-4078. For another example of unsymmetrical triyne synthesis, see: Gardner, J. N.; Jones, E. R. H.; Leeming, P. R.; Stephenson, J. S. J. Chem. Soc. 1960, 691-697.
85. For other examples of unsymmetrical diyne syntheses, see: (a) Alami, M.; Ferri, F. Tetrahedron Lett. 1996, 37, 2763-2766. (b) Kwon, J. H.; Lee, S. T.; Shim, S. C.; Hoshino, M. J. Org. Chem. 1994, 59, 1108-1114. (c) Aitken, R. A.; Seth, S. J. Chem. Soc., Perkin Trans. 1 1994, 2461-2466. (d) Blanco, L.; Helson, H. E.; Hirthammer, M.; Mestdagh, H.; Spyroudis, S.; Vollhardt, K. P. C. Angew. Chem., Int. Ed. Engl. 1987, 26, 1246-1247. (e) Ziegler, C. B., Jr.; Harris, S. M.; Baldwin, J. E. J. Org. Chem. 1987, 52, 443-446. (f) Fritzsche, U.; Hünig, S. Tetrahedron Lett. 1972, 4831-4834. (g) Lu, W.; Zheng, G.; Aisa, H. A.; Cai, J. Tetrahedron Lett. 1998, 39, 9521-9522. (h) Zheng, G.; Lu, W.; Cai, J. J. Nat. Prod. 1999, 62, 626-628. (i) Nishihara, Y.; Ikegashira, K.; Hirabayashi, K.; Ando, J.; Mori, A.; Hiyama, T. J. Org. Chem. 2000, 65, 1780-1787. (j) Nishihara, Y.; Ikegashira, K.; Mori, A.; Hiyama, T. Tetrahedron Lett. 1998, 39, 4075-4078. For another example of unsymmetrical triyne synthesis, see: Gardner, J. N.; Jones, E. R. H.; Leeming, P. R.; Stephenson, J. S. J. Chem. Soc. 1960, 691-697.
86. For a preliminary account of these results, see: Chernick, E. T.; Eisler, S.; Tykwinski, R. R. Tetrahedron Lett. 2001, 42, 8575-8578.
87. A similar route has been utilized by others; inter alia, see: (a) Brown, R. F. C.; Jackson, W. R.; McCarthy, T. D. Tetrahedron 1994, 50, 5469-5488. (b) Baldoli, C.; Del Buttero, P.; Licandro, E.; Maiorana, S.; Papagni, A.; Torchio, M. Tetrahedron Lett. 1993, 34, 7943-7946.
88. A similar route has been utilized by others; inter alia, see: (a) Brown, R. F. C.; Jackson, W. R.; McCarthy, T. D. Tetrahedron 1994, 50, 5469-5488. (b) Baldoli, C.; Del Buttero, P.; Licandro, E.; Maiorana, S.; Papagni, A.; Torchio, M. Tetrahedron Lett. 1993, 34, 7943-7946.
89. Lange, T.; van Loon, J.-D.; Tykwinski, R. R.; Schreiber, M.; Diederich, F. Synthesis 1996, 537-550.
90. (a) Corey, E. J.; Fuchs, P. L. Tetrahedron. Lett. 1972, 3769-3772.
91. (b) Posner, G.; Loomis, G. L.; Sawaya, H. S. Tetrahedron Lett. 1975, 1373-1376.
92. (c) Ramirez, F.; Desai, N. B.; McKelvie, N. J. Am. Chem. Soc. 1962, 84, 1745-1747.
93. (d) Neidlein, R.; Winter, M. Synthesis 1998, 1362-1366.
94. (e) Anthony, J.; Boldi, A. M.; Rubin, Y.; Hobi, M.; Gramlich, V.; Knobler, C. B.; Seiler, P.; Diederich, F. Helv. Chim. Acta 1995, 78, 13-45.
95. A recent report offers one potential solution to this problem; see: Rezaei, H.; Normant, J. F. Synthesis 2000, 109.
96. Köbrich had extensively studied solvent effects in aryl- and alkyl-substituted alkylidene carbenes; see: Köbrich, G.; Buck, P. In Chemistry of Acetylenes; Viehe, H. G., Ed.; Marcel Dekker: New York, 1969; Chapter 2.
97. A full investigation of the mechanistic aspects of these reactions is under way and will be published in due course. Preliminary evidence suggests that collapse of the carbenoid intermediate is consistent with that expected on the basis of the results of Curtin and Bothner-By, which is to say that the group that is trans to the bromide atom in the intermediate 2 is the one that migrates; see: Curtin, D. Y.; Flynn, E. W.; Nystrom, R. F. J. Am. Chem. Soc. 1958, 90, 4599. Bothner-By, A. A. J. Am. Chem. Soc. 1955, 77, 3293. See also ref 20a.
98. A full investigation of the mechanistic aspects of these reactions is under way and will be published in due course. Preliminary evidence suggests that collapse of the carbenoid intermediate is consistent with that expected on the basis of the results of Curtin and Bothner-By, which is to say that the group that is trans to the bromide atom in the intermediate 2 is the one that migrates; see: Curtin, D. Y.; Flynn, E. W.; Nystrom, R. F. J. Am. Chem. Soc. 1958, 90, 4599. Bothner-By, A. A. J. Am. Chem. Soc. 1955, 77, 3293. See also ref 20a.
99. Using TLC to monitor these reactions is problematic, as warming of the sample in the capillary tube used for TLC application can lead to the inaccurate observation that the reaction has reached completion.
100. Experimental evidence suggests that lithium-halogen exchange is faster than quenching of the BuLi by adventitious water in the reaction medium. As a result, any water that is present results in protonation of the carbenoid intermediate, which severely complicates purification due to very similar retention times on chromatographic supports.
101. The low yield for 8c results from the presence of the o-alkoxy substituent; see: Köbrich, G.; Trapp, H. Chem. Ber. 1966, 99, 680-688.
102. (a) Walton, D. R. M.; Waugh, F. J. Organomet. Chem. 1972, 37, 45-56.
103. (b) Suzuki, R.; Tsukuda, H.; Watanabe, N.; Kuwatani, Y.; Ueda, I. Tetrahedron 1998, 54, 2477-2496.
104. Shirakawa, H.; Masuda, T.; Takeda, K. In The Chemistry of Triple-bonded Functional Groups; Patai, S., Ed.; John Wiley and Sons: New York, 1994; Vol. 2, Suppl. 2, pp 992-994.
105. The general experimental details and characterization for all alcohols, ketones, and dibromoolefin precursors are detailed in the Supporting Information.
106. Wan, W. B.; Haley, M. M. J. Org. Chem. 2001, 66, 3893-3901.