Lewis Acid-Catalyzed Intramolecular [2 + 2] Cycloaddition of α-Ester-Substituted Conjugated Dienyl- And Trienylphosphonates. New Synthesis of Functionalized Cyclic Terpenoids

Journal of Organic Chemistry

Volumn 62, Issue 24, 1997, Pages 8419-8424

  Okauchi, Tatsuo ^a   Kakiuchi, Toshihito ^a   Kitamura, Naotaka ^a   Utsunomiya, Tomohisa ^a   Ichikawa, Junji ^a   Minami, Toru ^a  

^a KYUSHU INSTITUTE OF TECHNOLOGY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000736055     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo971153g     Document Type: Article

References (29)

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15. For the ene reaction of vinylphosphonates, see: (a) Albisetti, C. J.; Fisher, N. G.; Hogsed, M. J.; Joyce, R. M. J. Am. Chem. Soc. 1956, 78, 2637. (b) Snider, B. B.; Philips, G. B. J. Org. Chem. 1983, 48, 3685. (c) Sarker, T. K.; Rao, P. S. V. S. Synth. Commun. 1989, 19, 1281.
16. For the ene reaction of vinylphosphonates, see: (a) Albisetti, C. J.; Fisher, N. G.; Hogsed, M. J.; Joyce, R. M. J. Am. Chem. Soc. 1956, 78, 2637. (b) Snider, B. B.; Philips, G. B. J. Org. Chem. 1983, 48, 3685. (c) Sarker, T. K.; Rao, P. S. V. S. Synth. Commun. 1989, 19, 1281.
17. Recent papers, see: (a) Brengel, G. P.; Rithner, C.; Meyers, A. I. J. Org. Chem. 1994, 59, 5144. (b) Knölker, H.-J.; Baum, G.; Graf, R. Angew. Chem., Int. Ed. Engl. 1994, 33, 1612. (c) Monti, H.; Audran, G.; Léandri, G.; Monti, J.-P. Tetrahedron Lett. 1994, 35, 3073. (d) Narasaka, K.; Hayashi, Y.; Shimazu, H.; Niihata, S. J. Am. Chem. Soc. 1992, 114, 8869 and references therein.
18. Recent papers, see: (a) Brengel, G. P.; Rithner, C.; Meyers, A. I. J. Org. Chem. 1994, 59, 5144. (b) Knölker, H.-J.; Baum, G.; Graf, R. Angew. Chem., Int. Ed. Engl. 1994, 33, 1612. (c) Monti, H.; Audran, G.; Léandri, G.; Monti, J.-P. Tetrahedron Lett. 1994, 35, 3073. (d) Narasaka, K.; Hayashi, Y.; Shimazu, H.; Niihata, S. J. Am. Chem. Soc. 1992, 114, 8869 and references therein.
19. Recent papers, see: (a) Brengel, G. P.; Rithner, C.; Meyers, A. I. J. Org. Chem. 1994, 59, 5144. (b) Knölker, H.-J.; Baum, G.; Graf, R. Angew. Chem., Int. Ed. Engl. 1994, 33, 1612. (c) Monti, H.; Audran, G.; Léandri, G.; Monti, J.-P. Tetrahedron Lett. 1994, 35, 3073. (d) Narasaka, K.; Hayashi, Y.; Shimazu, H.; Niihata, S. J. Am. Chem. Soc. 1992, 114, 8869 and references therein.
20. Recent papers, see: (a) Brengel, G. P.; Rithner, C.; Meyers, A. I. J. Org. Chem. 1994, 59, 5144. (b) Knölker, H.-J.; Baum, G.; Graf, R. Angew. Chem., Int. Ed. Engl. 1994, 33, 1612. (c) Monti, H.; Audran, G.; Léandri, G.; Monti, J.-P. Tetrahedron Lett. 1994, 35, 3073. (d) Narasaka, K.; Hayashi, Y.; Shimazu, H.; Niihata, S. J. Am. Chem. Soc. 1992, 114, 8869 and references therein.
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22. 4.
23. The other set of transition states, in which 3′-methyl group is axial, are negligible, because of their 1,3-diaxial interaction.
24. A reviewer has proposed a steric argument that A is disfavored relative to B: the axial substituent at C1′ does not want to be over the cyclohexane ring.
25. (a) Snider, B. B. In Selectivities in Lewis Acid Promoted Reactions; Schinzer, D., Ed.; Kluwer Academic: Dordrecht, 1989; Chapter 8.
26. (b) Snider, B. B.; Rodini, D. J.; van Straten, J. J. Am. Chem. Soc. 1980, 102, 5872.
27. For the formation of 24a, 25a, and 24b, we tentatatively propose the following mechanistic possibility: (i) the Lewis acid-catalyzed intramolecular [2 + 2] cycloaddition of dienyl- and trienylphosphonates, 11 and 12, gives strained bicyclo[2.2.0]hexane intermediates B via zwitterionic [2 + 2] cycloadduct intermediates A. (ii) Ring opening of a cyclobutane ring, followed by double 1,2-hydride shifts (path a) and/or 1,3-hydride shift (path b) affords 24a, 25a and/ or 24b, respectively. Chemical equation presented One reviewer has proposed a following alternative mechanism: (i) a deprotonation of the dienyl- or trienylphosphonate occurs, followed by protonation of a prenyl moiety to give a tertiary cation; (ii) this cation cyclizes to 24 and a subsequent deprotonation/reprotonation gives 25. Another reviewer has explained the mechanism as follows: Lewis acid adds to the terminal trisubstituted double bond in the same manner a proton would. From the acyclic, cationic intermediate so obtained, 23 can result by chloride addition and replacement of the metal fragment by a proton. 24 and 25 are given from a 1,3,3-trimethylcyclohexyl cation formed by a cationic cyclization of this intermediate. We appreciate the suggestion of the reviewers on the possibility of these alternative mechanisms.
28. 13C chemical shift data with those of 21a and 21b.
29. Reetz, M. T.; Westermann, J.; Steinbach, R.; Wenderoth, B.; Peter, R.; Ostarek, R.; Maus, S. Chem. Ber. 1985, 118, 1421.