An ab initio study of the P-C bond rotation in phosphoryl- and thiophosphoryl-stabilized carbanions: Five- and six-membered heterocycles

Journal of Organic Chemistry

Volumn 61, Issue 24, 1996, Pages 8551-8563

  Kranz, Michael ^a   Denmark, Scott E ^a   Swiss, Kevin A ^a   Wilson, Scott R ^a  

^a UNIVERSITY OF ILLINOIS AT URBANA CHAMPAIGN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000803551     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9602783     Document Type: Article

References (45)

1. Denmark, S. E.; Chen, C.-T.; Reed, R. A. Adv. Carbanion Chem. Manuscript in preparation.
2. Kranz, M.; Denmark, S. E. J. Org. Chem. 1995, 60, 5867.
3. (a) Denmark, S. E.; Kim, J.-H. J. Org. Chem. 1995, 60, 7535.
4. (b) Denmark, S. E.; Kim, J.-H.; Pansare, S. V. Manuscript in preparation.
5. (c) Brice, L. J. Unpublished results from these laboratories.
6. Denmark, S. E.; Chen, C.-T. J. Am. Chem. Soc. 1995, 117, 11879.
7. (a) Cramer, C. J.; Denmark, S. E.; Miller, P. C.; Dorow, R. L.; Swiss, K. A.; Wilson, S. R. J. Am. Chem. Soc. 1994, 116, 2437.
8. (b) Denmark, S. E.; Dorow, R. L. J. Am. Chem. Soc. 1990, 112, 864.
9. (c) Denmark, S. E.; Miller, P. C.; Wilson, S. R. J. Am. Chem. Soc. 1991, 113, 1468.
10. (a) Denmark, S. E.; Swiss, K. A.; Wilson, S. R. J. Am. Chem. Soc. 1993, 115, 3826.
11. (b) Denmark, S. E.; Swiss, K. A. J. Am. Chem. Soc. 1993, 115, 12195.
12. (a) Schleyer, P. v. R.; Clark, T.; Kos, A. J.; Spitznagel, G. W.; Rohde, C.; Arat, D.; Houk, K. N.; Rondan, N. G. J. Am. Chem. Soc. 1984, 106, 6467.
13. See also: (b) Bernardi, F.; Bottoni, A.; Valli, G. S.; Venturini, A. Gazz. Chim. Ital. 1990, 120, 301. (c) El-Nahas, A. M.; Schleyer, P. v. R. J. Comput. Chem. 1994, 15, 596.
14. See also: (b) Bernardi, F.; Bottoni, A.; Valli, G. S.; Venturini, A. Gazz. Chim. Ital. 1990, 120, 301. (c) El-Nahas, A. M.; Schleyer, P. v. R. J. Comput. Chem. 1994, 15, 596.
15. Streitwieser, A., Jr.; Rajca, A.; McDowell, R. S.; Glaser, R. J. Am. Chem. Soc. 1987, 109, 4184.
16. Denmark, S. E.; Cramer, C. J. J. Org. Chem. 1990, 55, 1806.
17. Zarges, W.; Marsch, M.; Harms, K.; Haller, F.; Frenking, G.; Boche, G. Chem. Ber. 1991, 124, 861.
18. For a review of the bonding in phosphoryl and thiophosphoryl compounds, see: Gilheany, D. G. Chem. Rev. 1994, 94, 1339.
19. Hehre, W. J.; Radom, L.; Schleyer, P. v. R.; Pople, J. A. Ab Initio Molecular Orbital Theory; Wiley-Interscience: New York, 1986.
20. Gaussian92, Revision E2 and G3. 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, M. 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, Inc., Pittsburgh, PA, 1992.
21. Roothaan, C. C. J. Rev. Mod. Phys. 1951, 23, 69.
22. (a) Møller, C.; Plesset, M. S. Phys. Rev. 1934, 46, 618.
23. (b) Binkley, J. S.; Pople, J. A. Int. J. Quant. Chem. 1975, 9, 229.
24. Pople, J. A.; Krishnan, R.; Schlegel, H. B.; Binkley, J. S. Int. J. Quant. Chem. 1979, 13, 225.
25. (a) Glendening, E. D.; Reed, A. E.; Carpenter, J. E.; Weinhold, F. NBO Version 3.1.
26. (b) Reed, A. E.; Curtiss, L. A.; Weinhold, F. Chem. Rev. 1988, 88, 899.
27. Tyrrell, J.; Weinstock, R. B.; Weinhold, F. Int. J. Quant. Chem. 1981, 19, 781.
28. Arnaud, R. J. Comput. Chem. 1994, 15, 1341.
29. Kaushik, M. P.; Vaidyanathaswamy, R. J. Org. Chem. 1980, 45, 2270.
30. Swiss, K. A.; Denmark, S. E.; Wilson, S. R. Unpublished results.
31. 2 hybridized. (a) P=O acyclic: DOKZEI, JISYIT, JISYOZ, OMAPBD, VIJNOR. (b) P=S acyclic: DODDIJ, JEXJUR, KETJAU, KICFEH, PAFKUC, VEZKIU, YAGLOH. (c) P=O five ring cyclic: CUXDII, DOCSAK, JECYIZ, JOTFIH, JOTFON, KADMOR, KIVFEA.
32. There is a significant disorder in the THF molecules that leads to a modest wR2 value (0.152). The relevant part of the structure shows little variation.
33. - is not due to the different prefixed Li-X-P angles, the oxygen analog has been reoptimized with the Li-X-P bond angle from the sulfur X-ray structure (109.7°), which had a negligible influence on the relative energies.
34. (a) Hanessian, S.; Delorme, D.; Beaudoin, D.; Leblanc, Y. J. Am. Chem. Soc. 1984, 106, 5754.
35. (b) Hanessian, S.; Bennani, Y. L.; Delorme, D. Tetrahedron Lett. 1990, 31, 6461.
36. (c) Hanessian, S.; Bennani, Y. L. Tetrahedron Lett. 1990, 31, 6465.
37. (d) Hanessian, S.; Beaudoin, S. Tetrahedron Lett. 1992, 33, 7655.
38. (e) Hanessian, S.; Beaudoin, S. Tetrahedron Lett. 1992, 33, 7659.
39. (f) Hanessian, S.; Gomtsyan, A.; Payne, A.; Hervé, Y.; Beaudoin, S. J. Org. Chem. 1993, 58, 5032.
40. (g) Hanessian, S.; Bennani, Y. L.; Leblanc, Y. Heterocycles 1993, 35, 1411.
41. (h) Hanessian, S.; Gomtsyan, A. Tetrahedron Lett. 1994, 35, 7509.
42. (i) Hanessian, S.; Andreotti, D.; Gomtsyan, A. J. Am. Chem. Soc. 1995, 117, 10393.
43. NIMAG = number of imaginary frequencies in the Hessian matrix.
44. Due to the many fixed parameters in the molecules, we did not perform any higher level optimizations.
45. -, 111.2°). This is a general trend in coordination compounds with these phosphine chalcogens: Burford, N.; Royan, B. W.; Spence, R. E. v. H.; Rogers, R. D. J. Chem. Soc., Dalton Trans. 1990, 2111.