Competition between alkenes in intramolecular ketene-alkene [2 + 2] cycloaddition: What does it take to win?

Journal of Organic Chemistry

Volumn 70, Issue 1, 2005, Pages 291-296

  Bélanger, Guillaume ^a   Lévesque, François ^a   Pâquet, Julie ^a   Barbe, Guillaume ^a  

^a UNIVERSITÉ DE SHERBROOKE   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

ADDITION REACTIONS; AROMATIC COMPOUNDS; CHEMICAL BONDS;

CYCLOADDIATION; HAMMET CONSTANT; KETENES; TETHERING;

OLEFINS;

ALKENE; KETENE DERIVATIVE;

ARTICLE; ASYMMETRIC SYNTHESIS; CHEMICAL REACTION KINETICS; CHEMICAL STRUCTURE; CROSS LINKING; CYCLOADDITION; EXPERIMENT; METHODOLOGY; MOLECULE;

EID: 11844253817     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo0483466     Document Type: Article

References (43)

1. Staudinger, H. Chem. Ber. 1905, 38, 1735-1739.
2. For a review on proposed [2 + 2] cycloaddition mechanisms of ketenes with alkenes, see: Tidwell, T. T. Ketenes; Wiley: New York, 1995; pp 486-502, and references therein.
3. (a) Corey, E. J.; Arnold, Z.; Hutton, J. Tetrahedron Lett. 1970, 307-310.
4. (b) Wagner, H. U.; Gompper, R. Tetrahedron Lett. 1970, 2819-2822.
5. (c) Gompper, R. Angew. Chem., Int. Ed. Engl. 1969, 8, 312-327.
6. (d) Becker, D.; Brodsky, N. C. J. Chem. Soc., Chem. Commun. 1978, 237-238.
7. (a) Fleming, I. Frontier Orbitals and Organic Chemical Reactions; Wiley: New York, 1976; pp 110-148.
8. (b) Woodward, R. B.; Hoffmann, R. Angew. Chem., Int. Ed, Engl. 1969, 8, 781-853.
9. (c) Woodward, R. B.; Hoffmann, R. The Conservation of Orbital Symmetry; Verlag Chimie/Academic: New York, 1970.
10. For calculations of transition states for ketene-alkene [2 + 2] cycloadditions, see: (a) Bernardi, F.; Bottoni, A.; Robb, M. A.; Venturini, A. J. Am. Chem. Soc. 1990, 112, 2106-2114. (b) Wang, X.; Houk, K. N. J. Am. Chem. Soc. 1990, 112, 1754-1756.
11. For calculations of transition states for ketene-alkene [2 + 2] cycloadditions, see: (a) Bernardi, F.; Bottoni, A.; Robb, M. A.; Venturini, A. J. Am. Chem. Soc. 1990, 112, 2106-2114. (b) Wang, X.; Houk, K. N. J. Am. Chem. Soc. 1990, 112, 1754-1756.
12. For a review on intramolecular ketene-alkene [2 + 2] cycloadditions, see: Snider. B. B. Chem. Rev. 1988, 88, 793-811.
13. (a) Markó, I.; Ronsmans, B.; Hesbian-Frisque, A.-M.; Dumas, S.; Ghosez, L. J. Am. Chem. Soc. 1985, 107, 2192-2194.
14. (b) Snider, B. B.; Hui, R. A. H. F.; Kulkarni, Y. S. J. Am. Chem. Soc. 1985, 107, 2194-2196.
15. (c) Brady, W. T.; Giang, Y. F. J. Org. Chem. 1985, 50, 5177-5179.
16. (d) Intramolecular [2 + 2] cycloadditions using ketene iminiums have been for different ring sizes: Brady, W. T.; Giang, Y. F.; Weng, L.; Dad, M. M. J. Org. Chem. 1987, 52, 2216-2220.
17. (a) Baldwin, J. E.; Kapecki, J. A. J. Am. Chem. Soc. 1970, 92, 4868-4873.
18. (b) For the ketenes' preference for electron-rich alkenes, see also: Brady, W. T.; O'Neal, H. R. J. Org. Chem. 1967, 32, 2704-2707.
19. 23 thus casting doubt on the validity of the reported ρ value.
20. Snider, B. B.; Vo, N. H.; Foxman, B. M. J. Org. Chem. 1993, 58, 7228-7237.
21. 8
22. Trans-1,2-disubstituted alkenes react more quickly than cis-1,2-disubstituted alkenes with ketenes in intramolecular [2 + 2] cycloadditions, due to steric reasons. See: (a) Huisgen, R.; Mayr, H. Tetrahedron Lett. 1975, 16, 2965-2968. (b) Snider, B. B. Walner, M. B. Tetrahedron 1989, 45, 3171-3182. (c) Snider, B. B., Allentoff, A. J., Walner, M. B. Tetrahedron 1990, 46, 8031-8042. Also, we wanted to diminish the chance of side reactions, such as alkene isomerization, in the cycloaddition step, which occurs at elevated temperature (refluxing toluene).
23. Trans-1,2-disubstituted alkenes react more quickly than cis-1,2-disubstituted alkenes with ketenes in intramolecular [2 + 2] cycloadditions, due to steric reasons. See: (a) Huisgen, R.; Mayr, H. Tetrahedron Lett. 1975, 16, 2965-2968. (b) Snider, B. B. Walner, M. B. Tetrahedron 1989, 45, 3171-3182. (c) Snider, B. B., Allentoff, A. J., Walner, M. B. Tetrahedron 1990, 46, 8031-8042. Also, we wanted to diminish the chance of side reactions, such as alkene isomerization, in the cycloaddition step, which occurs at elevated temperature (refluxing toluene).
24. Trans-1,2-disubstituted alkenes react more quickly than cis-1,2-disubstituted alkenes with ketenes in intramolecular [2 + 2] cycloadditions, due to steric reasons. See: (a) Huisgen, R.; Mayr, H. Tetrahedron Lett. 1975, 16, 2965-2968. (b) Snider, B. B. Walner, M. B. Tetrahedron 1989, 45, 3171-3182. (c) Snider, B. B., Allentoff, A. J., Walner, M. B. Tetrahedron 1990, 46, 8031-8042. Also, we wanted to diminish the chance of side reactions, such as alkene isomerization, in the cycloaddition step, which occurs at elevated temperature (refluxing toluene).
25. Hrubowchak, D. M.; Smith, F. X. Tetrahedron Lett. 1983, 24, 4951-4954.
26. For cis alkenes, used in other sequences of reactions that are not mentioned in this paper, this step gave partial isomerization.
27. Even with careful manipulations, traces of water could generate an anhydride from two molecules of acyl chloride. The formation of anhydride occurs during the ketene formation step, when the acyl chloride is heated in the presence of triethylamine. The acyl chloride formation itself is clean and usually quantitative. The amount of anhydride observed is greater when the alkenes are deactivated toward the [2 + 2] cycloaddition with the ketene.
28. 1H coupling, typically over three to four bonds.
29. 13C coupling over one bond.
30. 13C coupling, typically over two to three bonds.
31. The spectral evidence that allowed us to assign the structure as being 19 is discussed in detail in the Supporting Information, section V.
32. Muir, J. C.; Pattenden, G.; Ye, T. J. Chem. Soc., Perkin Trans. 1 2002, 2243-2250.
33. Hansch, C.; Leo, A.; Taft, W. Chem. Rev. 1991, 91, 165-195 and references therein.
34. 2 triplet at 3.18 ppm.
35. 1H NMR spectra of isolated and purified 24e and 25e in the Supporting Information.
36. 4 times faster than the dimerization rate in a 1 M solution (Streitwieser, A., Jr Solvotic Displacement Reactions; McGraw-Hill: New York, 1962; p 105), or 200 000 times faster in a 0.055 M solution. Although the folding of the molecule for this 5-exo-tet cyclization is not the same as for the [2 + 2] cycloaddition, it is nonetheless an indication that the intermolecular reaction should be negligible.
37. 0) calculation. See also: Logan, S. Introduction à la cinétique chimique; Dunod: Paris, 1998; pp 47-50. Schaal, R. Chemical Kinetics of Homogeneous Systems, D. Riedel: Dordrecht, The Netherlands, 1974; pp 30-32.
38. 0) calculation. See also: Logan, S. Introduction à la cinétique chimique; Dunod: Paris, 1998; pp 47-50. Schaal, R. Chemical Kinetics of Homogeneous Systems, D. Riedel: Dordrecht, The Netherlands, 1974; pp 30-32.
39. As a criterion of linearity, the correlation coefficient r is required to be at least 0.95 and preferably above 0.98. See: Connors, K. A. Chemical Kinetics; VCH: New York, 1990; pp 315-320.
40. 0) graph.
41. The characterization is identical with that reported for the same compound, but prepared through another route. See: Prat, M.; Moreno-Mañas, M.; Ribas, J. Tetrahedron 1988, 44, 7205-7212.
42. The characterization is identical with that reported for the same compound, but prepared through another route. See: Arnold, R. T.; Kulenovic, S. T. J. Org. Chem. 1980, 45, 891-894.
43. See: Ren, X. F.; Turos, E.; Lake, C. H.; Churchill, M. R. J. Org. Chem. 1995, 60, 6468-6483.