The effect of carbonyl substitution on the strain energy of small ring compounds and their six-member ring reference compounds

Journal of the American Chemical Society

Volumn 128, Issue 14, 2006, Pages 4598-4611

  Bach, Robert D ^a   Dmitrenko, Olga ^a  

^a UNIVERSITY OF DELAWARE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CHEMICAL BONDS; PARAFFINS; PHOSPHORUS; STRAIN; SULFUR;

CYCLOHEXANONE; DISSOCIATION ENERGIES; RING COMPOUNDS; STRAIN ENERGIES;

AROMATIC COMPOUNDS;

CARBONYL DERIVATIVE; CYCLOHEXANE; CYCLOHEXANONE; CYCLOPROPANE; HYDROCARBON; LACTAM; LACTONE; PHOSPHORUS;

AB INITIO CALCULATION; ARTICLE; DISSOCIATION; ENERGY; THERMODYNAMICS;

CYCLOHEXANES; CYCLOPROPANES; ETHYLENE OXIDE; LACTAMS; LACTONES; STRUCTURE-ACTIVITY RELATIONSHIP; THERMODYNAMICS;

EID: 33646034346     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja055086g     Document Type: Article

References (49)

1. For recent discussions of the methods for the calculation of ring strain energies, see: (a) Khoury, P. R.; Goddard, J. D.; Tam, W. Tetrahedron 2004, 60, 8103.
2. (b) Alcami, M.; Mo, O.; Yanez, M. J. Comput. Chem. 1998, 19, 1072 and references therein.
3. (c) Cremer, D.; Kraka, E. In Theoretical Models of the Chemical Bond: Maksic, Z. B., Ed.; Springer: Heidelberg, 1990; Vol. 2, p 453.
4. (d) Dudev, T.; Lim, C. J. Am. Chem. Soc. 1998, 120, 4450.
5. (a) Benson, S. W.; Cruickshank, F. R.; Golden, D. M.; Haugen, G. R.; O'Neil, H. E.; Rogers, A. S.: Shaw, R.; Walsh, R. Chem. Rev. 1969, 69, 279.
6. (b) NIST Standard Reference Database, No. 69, June 2005 (http:// webbook.nist.gov/chemistry.)
7. For an excellent discussion of the various heat of formation group increments, see: Schleyer, P. v R.; Williams, J. E.; Blanchard, K. R. J. Am. Chem. 1970, 92, 2377.
8. (a) Wiberg, K. W. Angew. Chem., Int. Ed. Engl. 1986, 25, 312.
9. (b) Wiberg, K. W.; Fenoglio, R. A. J. Am. Chem. Soc. 1968, 90, 3395.
10. (c) Eliel, E. L.; Wilen, S. H. Stereochemistry of Organic Chemistry; Wiley: New York, 1994; pp 676-678, 732.
11. Johnson, W. T. G.; Borden, W. T. J. Am. Chem. Soc. 1997, 119, 5930.
12. (a) Bach, R. D.; Dmitrenko, O. J. Am. Chem. Soc. 2004, 126, 4444.
13. (b) Bach, R. D.; Dmitrenko, O. J. Org. Chem. 2002, 67, 2588.
14. (c) Bach, R. D.; Dmitrenko, O. J. Org. Chem. 2002, 67, 3884.
15. For a recent critical evaluation of the schemes used to calculate intrinsic bond energies (BE) leading to new estimates of the stabilization of cyclopropane due to C-H bond strengthening, see: Exner, K.; Schleyer, P. v. R. J. Phys. Chem. A 2001, 105, 3407.
16. Baghal-Vayjooee, M. H.; Benson, S. W. J. Am. Chem. Soc. 1979, 101, 2838.
17. (a) Rodriquez, C. F.; Williams, I. H. J. Chem. Soc., Perkin Trans. 2 1997, 953.
18. (b) Ruggiero, G. D.; Williams, I. H. J. Chem. Soc., Perkin Trans. 2 2001, 733.
19. (c) Buchanan, G. J.; Charlton, M. H.; Mahon, M. F.; Robinson, J. J.; Ruggiero, G. D.; Williams, I. H. J. Phys. Org. Chem. 2002, 15, 642.
20. f,298= -47.3 kcal/ mol),9e we estimate an SE for oxiranone (based upon an SE for oxirane of 27.25 kcal/mol) of 39 kcal/mol, in excellent with earlier value suggested by Williams using the MP2/6-311G(d,p) method.
21. (e) Schröder, D.; Goldberg, N.; Zurnmack, W.; Schwarz, H.; Poutsma, J. C.; Squires, R. R. Int. J. Mass Spectrom. Ion Processes 1997, 165/166, 71.
22. (a) Frisch, M. J.; et al. Gaussian 98, revision A.7; Gaussian, Inc.: Pittsburgh, PA, 1998;
23. (b) Gaussian 03, revision B.05 (SGI64-G03RevB.05); Gaussian, Inc.: Pittsburgh, PA, 2003. See the Supporting Information for the full list of authors.
24. (a) Schlegel, H. B. J. Comput. Chem. 1982, 3, 214.
25. (b) Schlegel, H. B. Adv. Chem. Phys. 1987, 67, 249.
26. (c) Schlegel, H. B. In Modern Electronic Structure Theory; Yarkony, D. R., Ed.; World Scientific: Singapore, 1995; p 459.
27. (a) Curtiss, L. A.; Raghavachari, K.; Trucks, G. W.; Pople, J. A. J. Chem. Phys. 1991, 94, 7221.
28. (b) Curtiss, L. A.; Raghavachari, K.; Pople, J. A. J. Chem. Phys. 1997, 106, 1063.
29. (c) Ochterski, J. W.; Petersson, G. A.; Montgomery, J. A. J. Chem. Phys. 1996, 104, 2598.
30. (d) Curtiss, L. A.; Raghavachari, K.; Redfern, P. C.; Rassolov, V.; Pople, J. A. J. Chem. Phys. 1998, 109, 7764.
31. For approaches to calculate these two nonobservable contributors, BE and R, which are not directly measurable for molecules of this type, see: (a) Bader, R. F. W.; Tang, T.-H.; Tal, Y.; Biegler-Konig, F. W. J. Am. Chem. Soc. 1982, 104, 946.
32. (b) Bader, R. F. W. Atoms In Molecules: A Quantum Theory; Oxford University Press: Oxford, 1990.
33. (c) Grimme, S. J. Am. Chem. Soc. 1996, 118, 1529.
34. (d) Krygowski, T. M.; Ciesielski, A.; Bird, C. W.; Kotschy, A. J. Chem. Inf. Comput. Sci. 1995, 35, 203.
35. (e) Howard, S. T.; Cyranski, M. K.; Stolarczyk, L. Z. J. Chem. Soc., Chem. Commun. 2001, 197.
36. (a) Skancke, A.; Van Vechten, D.; Liebman, J. F.; Skancke, P. N. J. Mol. Struct. 1996, 376, 461 and references therein.
37. (b) Liebman, J. F.; Skancke, P. N. Int. J. Quantum Chem. 1996, 55, 707.
38. (c) Zeiger, D. N.; Liebman, J. F. J. Mol. Struct. 2000, 556, 83.
39. (d) Skancke, A.; Liebman, J. F. J. Org. Chem. 1999, 64, 6361.
40. 2A″ state), resulting in a stabilization energy of 23.1 kcal/mol (G3) due to electron delocalization in the π system. For a discussion, see: Bach, R. D.; Ayala, P. Y.; Schlegel, H. B. J. Am. Chem. Soc. 1996, 118, 12758.
41. Leopold, D. G.; Murray, K. K.; Miller, A. E. S.; Lineberger, W. C. J. Chem. Phys. 1985, 83, 4849.
42. For a description of the details for cyclization of n-hexane to cyclohexane, see ref 1d. For a series of parameters used for cyclization of a variety of substrates at the G2 level, see ref 6c.
43. For earlier examples of the use of homodesmotic reactions, see: (a) George, P.; Trachtman, M.; Bock, C. W.; Brett, A. M. Tetrahedron 1976, 32, 317.
44. (b) George, P.; Trachtman, M.; Brett, A. M.; Bock, C. W. J. Chem. Soc., Perkins Trans. 2 1977, 1036.
45. Bachrach, S. M. J. Chem. Educ. 1990, 67, 907.
46. Feng, Y.; Liu, L.; Wang, J. T.; Huang, H.; Guo, Q. X. J. Chem. Inf. Comput. Sci. 2003, 43, 2005.
47. f(298) for 3-pentanone and n-pentane are -61.8 and -35.08 kcal/mol, respectively. The reaction energy is very close to that reported in ref 9a (15.5 kcal/mol) based upon a similar exercise.
48. Bach, R. D.; Dmitrenko, O.; Adam, W.; Schambony, S. J. Am. Chem. Soc. 2003, 125, 924.
49. Bobek, M. M.; Krois, D.; Brehmer, T. H.; Giester, G.; Wiberg, K. B.; Brinker, U. H. J. Org. Chem. 2003, 68, 2129.