Development of Molecular Mechanics Torsion Parameters for α,β-Cyclopropyl α′,β′-Enones and Conformational Analysis of Bicyclo[m.1.0]alk-3-en-2-ones

Journal of Organic Chemistry

Volumn 62, Issue 11, 1997, Pages 3715-3721

  Mash, Eugene A ^a   Gregg, Timothy M ^a   Stahl, Matthew T ^a  

^a University of Arizona   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0345662455     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo962215q     Document Type: Article

References (31)

1. Mash, E. A.; Gregg, T. M.; Stahl, M. T.; Walters, W. P. J. Org. Chem. 1996, 61, 2738-2742.
2. (a) Mash, E. A.; Kaczynski, M. A.; Dolata, D. P. Tetrahedron Lett. 1990, 31, 4565-4568.
3. (b) Mash, E. A.; Gregg, T. M.; Kaczynski, M. A. J. Org. Chem. 1996, 61, 2743-2752.
4. For classification of rings by size, see: Eliel, E. L.; Wilen, S. H.; Mander, L. N. Stereochemistry of Organic Compounds; John Wiley & Sons: New York, 1994, pp 678.
5. Enantiomerically enriched bicyclo[m.1.0]alkan-2-ones 1 are readily prepared from 2-cycloalken-1-one ketals, see: (a) Mash, E. A.; Nelson, K. A. Tetrahedron 1987, 43, 679-692. (b) Mash, E. A.; Torok, D. S. J. Org. Chem. 1989, 54, 250-253. (c) Mash, E. A.; Math, S. K.; Arterburn, J. A. J. Org. Chem. 1989, 54, 4951-4953.
6. Enantiomerically enriched bicyclo[m.1.0]alkan-2-ones 1 are readily prepared from 2-cycloalken-1-one ketals, see: (a) Mash, E. A.; Nelson, K. A. Tetrahedron 1987, 43, 679-692. (b) Mash, E. A.; Torok, D. S. J. Org. Chem. 1989, 54, 250-253. (c) Mash, E. A.; Math, S. K.; Arterburn, J. A. J. Org. Chem. 1989, 54, 4951-4953.
7. Enantiomerically enriched bicyclo[m.1.0]alkan-2-ones 1 are readily prepared from 2-cycloalken-1-one ketals, see: (a) Mash, E. A.; Nelson, K. A. Tetrahedron 1987, 43, 679-692. (b) Mash, E. A.; Torok, D. S. J. Org. Chem. 1989, 54, 250-253. (c) Mash, E. A.; Math, S. K.; Arterburn, J. A. J. Org. Chem. 1989, 54, 4951-4953.
8. (a) Kamernitzky, A. V.; Akhrem, A. A. Tetrahedron 1962, 18, 705-750 and references cited therein,
9. (b) Houk, K. N.; Paddon-Row, M. N.; Rondan, N. G.; Wu, Y.-D.; Brown, F. K.; Spellmeyer, D. C.; Metz, J. T.; Li, Y.; Loncharich, R. J. Science 1986, 231, 1108-1117.
10. (c) Lowry, T. H.; Richardson, K. S. Mechanism and Theory in Organic Chemistry; 3rd ed.; Harper & Row: New York, 1987, pp 661-693 and references cited therein.
11. (d) Wu, Y.-D.; Houk, K. N.; Florez, J.; Trost, B. M. J. Org. Chem. 1991, 56, 3656-3664.
12. (e) Eksterowicz, J. E.; Houk, K. N. Chem. Rev. 1993, 93, 2439-2461.
13. Perlmutter, P. Conjugate Addition Reactions in Organic Synthesis, Pergamon Press: Oxford, 1992. Chapters 1 and 3.
14. (a) BATCHMIN, 4.0; Columbia University: New York, 1993.
15. (b) Mohamadi, F.; Richards, N. G. J.; Guida, W. C.; Liskamp, R.; Lipton, M.; Caufield, C.; Chang, G.; Hendrickson, T.; Still, W. C. J. Comput. Chem. 1990, 11, 440-467.
16. Spartan, 4.0; Wavefunction, Inc.: Irvine, CA, 1995.
17. To the best of our knowledge, no experimental or theoretical data pertaining to the torsional barriers in cyclopropyl vinyl ketone (5) has appeared in the literature.
18. 2 = 180°) due to severe steric interactions.
19. Frisch, M. J.; Trucks, G. W.; Head-Gordon, M.; Gill, P. M. W.; Wong, M. W.; Foresman, J. B.; Johnson, B. G.; Schlegel, H. B.; Robb, M. A.; Replogle, E. S.; Gomperts, R.; Andres, J. L.; Raghavachari, K.; Binkley, J. S.; Gonzalez, C.; Martin, R. L.; Fox, D. J.; Defrees, D. J.; Baker, J.; Stewart, J. J. P.; Pople, J. A. Gaussian 92, Revision G.2; Gaussian, Inc.: Pittsburgh, 1992.
20. Each of the bicyclo[m.1.0]alk-3-en-2-ones is hereafter given a number and a two-letter designation for purposes of rapid identification. The number refers to the larger ring size, the first letter to the relative stereochemistry about the cyclopropane, and the second letter to the relative stereochemistry about the alkene. Thus, 12ct refers to a bicyclo[10.1.0]tridec-3-en-2-one in which the relative stereochemistry about the cyclopropane is cis and the relative stereochemistry about the alkene is trans.
21. (a) Burkert, U.; Allinger, N. L. Molecular Mechanics; American Chemical Society: Washington, DC, 1982.
22. (b) Saunders, M. J. Am. Chem. Soc. 1987, 109, 3150-3152.
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24. (d) Saunders, M. J. Comput. Chem. 1989, 10, 203-208.
25. (e) Leach, A. R. In Rev. Comput. Chem.; K. B. Lipkowitz and D. B. Boyd, Eds.; VCH Publishers, Inc.: New York, 1991; Vol. 2; pp 1-55.
26. 2, respectively, are near °.
27. The six lowest energy conformers for each bicycle studied are depicted in the supporting information which accompanies this article.
28. (a) Bürgi, H. B.; Dunitz, J. D.; Lehn, J. M.; Wipff, G. Tetrahedron 1974, 30, 1563-1572.
29. (b) Bürgi, H.-B. Angew. Chem., Int. Ed. Engl. 1975, 14, 460-473.
30. See ref 3, p 654 and accompanying discussion.
31. Gregg, T. M. Ph.D. Dissertation, The University of Arizona, 1995.