Epoxidation of acyclic chiral allylic alcohols with peroxy acids: Spiro or planar butterfly transition structures? A computational DFT answer

Journal of Organic Chemistry

Volumn 65, Issue 7, 2000, Pages 2030-2042

  Freccero, Mauro ^a   Gandolfi, Remo ^a   Sarzi Amadè, Mirko ^a   Rastelli, Augusto ^b  

^a UNIVERSITY OF PAVIA   (Italy)

^b UNIVERSITY OF MODENA AND REGGIO EMILIA   (Italy)

Author keywords

[No Author keywords available]

Indexed keywords

ALLYL ALCOHOL; EPOXIDE; PERACETIC ACID; PERACID; SPIRO COMPOUND; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; CHIRALITY; CONFORMATIONAL TRANSITION; EPOXIDATION; HYDROGEN BOND; MOLECULAR STABILITY;

EID: 0034616182     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo991530k     Document Type: Article

References (54)

1. Bartlett, P. D. Rec. Chem. Prog. II 1950, 47.
2. (a) Bach, R. D.; Glukhovtsev, M. N.; Gonzales, C.; Marquez, M.; Estevez, C. M.; Baboul, A. G.; Schlegel, H. B. J. Phys. Chem. A 1997, 101, 6092.
3. (b) Bach, R. D.; Glukhovtsev, M. N.; Gonzales, C. J. Am. Chem. Soc. 1998, 120, 9902.
4. (a) Singleton, D. A.; Merrigan, S. R.; Liu, J.; Houk, K. N. J. Am. Chem. Soc. 1891, 119, 3385.
5. (b) Houk, K. N.; Liu, J.; DeMello, N. C.; Condroski, K. R. J. Am. Chem. Soc. 1997, 119, 10147.
6. (a) Koener, T.; Slebocka-Tilk, H.; Brown R. S. J. Org. Chem. 1999, 64, 196.
7. (b) Rebek, J., Jr.; Marshall, L.; McManis, J.; Wolak, R. J. Org. Chem. 1986, 51, 1649.
8. Henbest, H. B.; Wilson, R. A. L. J. Chem. Soc. 1959, 1958.
9. Itoh, T.; Jitsukawa, K.; Kaneda, K.; Teranishi, S. J. Am. Chem. Soc. 1979, 101, 159.
10. Chamberlain, P.; Roberts, M. L.; Whitham, G. H. J. Chem. Soc. B 1970, 1374.
11. Johnson, M. R.; Kishi, Y. Tetrahedron Lett. 1979, 4347.
12. (a) Sharpless, K. B.; Verhoeven, T. R. Aldrichimica Acta 1979, 12, 63.
13. (b) Sharpless, K. B.; Rossiter, B. E.; Verhoeven T. R. Tetrahedron Lett. 1979, 4733.
14. Kocovsky, P.; Stary, I. J. Org. Chem. 1990, 55, 3236.
15. Hoveyda, A. H.; Evans, D. A.; Fu, G. C. Chem. Rev. 1993, 93, 1307.
16. Narula, A. S. Tetrahedron Lett. 1983, 24, 5421.
17. (a) Adam, W.; Nestler, B. Tetrahedron Lett. 1993, 34, 611.
18. (b) Adam, W.; Smerz, A. K. J. Org. Chem. 1996, 61, 3506.
19. Adam, W.; Kumar, R.; Reddy, I.; Renz, M. Angew. Chem., Int. Ed. Engl. 1996, 35, 880.
20. Adam, W.; Corma, A.; Reddy, I.; Renz, M. J. Org. Chem. 1997, 62, 3631.
21. (e) Adam, W.; Stegmann, V. R.; Saha-Moller, C. R. J. Am. Chem. Soc. 1999, 121, 1879.
22. (f) Adam, W.; Mitchell, C. M.; Saha-Moller, C. R. J. Org. Chem. 1999, 64, 3699.
23. (g) Adam, W.; Degen, H. G.; Saha-Moller, C. R. J. Org. Chem. 1999, 64, 1274.
24. (h) Adam, W.; Prechtl, F.; Richter, M. J.; Smerz, A. K. Tetrahedron Lett. 1993, 34, 8427.
25. Adam, W.; Smerz, A. K Tetrahedron 1995, 51, 13039.
26. (j) Adam, W.; Brunker, H.; Kumar, A. S.; Peters, E. A.; Peters, K.; Schneider, U.; von Schnering, H. G. J. Am. Chem. Soc. 1996, 118, 1899.
27. (k) Adam, W.; Paredes, R.; Smerz, A. K.; Veloza, A. L. Liebigs Ann. / Recl. 1997, 547.
28. (l) Adam, W.; Paredes, R.; Smerz, A. K.; Veloza, A. Eur. J. Org. Chem. 1998, 349.
29. (m) Adam, W.; Mitchell, C. M.; Saha-Moller, C. R. Eur. J. Org. Chem. 1999, 785.
30. (n) Note added in proof: in a recent review (Adam, W.; Wirth, T. Acc. Chem. Res. 1999, 32, 703) Adam et al., while maintaining a "planar" geometry for peroxy acid epoxidation TSs, adopt a "Bach" model for hydrogen bonding; i.e., they now prefer hydrogen bond to peroxy acid carbonyl oxygen.
31. Kluge, R.; Schulz, M.; Liebsch, S. Tetrahedron 1996, 52, 2957.
32. Kende, A. S.; Delair, P.; Blass, B. E. Tetrahedron Lett. 1994, 35, 8123.
33. Chautemps, P.; Pierre, J. L. Tetrahedron 1976, 32, 549.
34. Bach, R. D.; Estévez, C. M.; Winter J. E.; Glukhovtsev, M. N. J. Am. Chem. Soc. 1998, 120, 680.
35. Freccero, M.; Gandolfi, R.; Sarzi-Amadè, M.; Rastelli, A. J. Org. Chem. 1999, 64, 3853.
36. For previous PM3 and B3LYP studies, respectively, on facial selectivity of cyclic alkenes see ref 20a and 20b.
37. (a) Lucero, M.; Houk, K. N. J. Org. Chem. 1998, 63, 6973.
38. (b) Freccero, M.; Gandolfi, R.; Sarzi-Amadè, M. Tetrahedron 1999, 55, 11309.
39. Becke, A. D. J. Chem. Phys. 1993, 98, 1372.
40. Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785.
41. (a) Freccero, M.; Gandolfi, R.; Sarzi-Amadè, M.; Rastelli, R. Tetrahedron 1998, 54, 6123.
42. (b) Freccero, M.; Gandolfi, R.; Sarzi-Amadè, M.; Rastelli, A. Tetrahedron 1998, 54, 12323.
43. Castejon, H.; Wiberg, K. B. J. Am. Chem. Soc. 1999, 121, 2139.
44. Pan, Y.; McAllister, M. A. J. Am. Chem. Soc. 1998, 120, 166.
45. The cc-pVTZ basis sets have been suggested by a reviewer to be "proper" for hydrogen bonding description. However, they are highly time-consuming, specially after inclusion of diffuse functions, and out of reach, at least for us, for relatively large systems such as those studied in this work. For this reason, we used the B3LYP/6-311+G** level for single-point calculations on B3LYP/6-31G* geometries as an acceptable compromise between reliability and time request. However, the reader should keep in mind that this basis set might slightly overestimate (see Table 1) the stability of exo-TS (with hydrogen bonding to peroxy oxygens) as compared to that of their endo counterpart (with hydrogen bonding to carbonyl oxygen).
46. Gaussian 94: Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gll, P. M. W.; Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Keith, T.; Peterson, G. A.; Montgomery, J. A.; Raghavachari, K.; Al-Laham, M. A.; Zakrzewski, V. G.; Ortiz, J. V.; Foresman, J. B.; Cioslowski, J.; Stefanov, B. B.; Nanayakkara, A.; Challacombe, M.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; Wong, M. W.; Andres, J. L.; Replogle, E. S.; Gompert, R.; Martin, R. L.; Fox, D. J.; Binkley, J. S.; Defrees, D. J.; Baker, J.; Stewart, J. P.; Head-Gordon, M.; Gonzales C.; Pople, J. A. Gaussian, Inc., Pittsburgh, PA, 1995.
47. Gaussian 98, Revision A.6: Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A., Jr.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Andres, J. L.; Gonzalez, C.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian, Inc., Pittsburgh, PA, 1998.
48. 7 plane by ≥55° and ≥11°, respectively). This distortion obviously compounds the spiro/planar TS classification.
49. Rastelli, A.; Bagatti, M.; Gandolfi, R. J. Am. Chem. Soc. 1995, 117, 4965.
50. Solvent effects (both absolute and relative) evaluated by this method are smaller than those obtained with the Tomasi method (as implemented in Gaussian 94) previously used by us. Because the performance of methods in evaluating the solvent effects is not, to date, satisfactorily assessed the "computed solvent effect" should be taken with some caution.
51. We did not try to locate the related conformational minima with the hydroxylic hydrogen pointing away from the π bond. Conformational analysis of 2-propenol clearly demonstrated that conformers of this type (without hydrogen bonding interactions and with repulsive closed shell interactions between lone pairs and the π bond) are definitely less stable than those in which hydrogen bonding operates.
52. Obviously our system behaves as a Curtin-Hammett system. The conformational equilibrium of the starting alcohols is very fast and product distribution is only determined by the relative TS energies. Thus, to calculate theoretical face selectivity one does not need to know which conformer each TS originates from.
53. 9 as a whole = +0.07 (+0.04). Electron transfer, from olefin to PFA, according to CHelpG analisys is -0.29 and -0.31 in syn,exo,threo-15a and syn,exo,erythro-22d, respectively.
54. 6 peroxy acid plane is always very close to being orthogonal to C=C bond.