Staggered Models for Asymmetric Induction: Attack Trajectories and Conformations of Allylic Bonds from ab Initio Transition Structures of Addition Reactions

Journal of the American Chemical Society

Volumn 104, Issue 25, 1982, Pages 7162-7166

  Paddon Row, Michael N ^a   Rondan, Nelson G ^a   Houk, K N ^a  

^a UNIVERSITY OF PITTSBURGH   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 15844390521     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00389a045     Document Type: Article

References (44)

1. For a general survey, see: Morrison, J. D.; Mosher, H. S. “Asymmetric Organic Reactions”; Prentice-Hall: New York, 1971; reprinted by the Americal Chemical Society, 1976.
2. Bartlett, P. A. Tetrahedron 1980, 36, 2.
3. Cram, D. J.; Abd Elhafez, F. A. J. Am. Chem. Soc. 1952, 74, 5828.
4. Karabatsos, G. J. J. Am. Chem. Soc. 1967, 89, 1367.
5. Cherest, M.; Felkin, H.; Prudent, N. Tetrahedron Lett. 1968, 2199, 2205.
6. Anh, N. T.; Eisenstein, O. Nouv. J. Chim. 1977, 1, 61.
7. Anh, N. T. Fortschr. Chem. Forsch. 1980, 88, 145.
8. Chautemps, P.; Pierre, J.-L. Tetrahedron 1976, 32, 549. Different X-eclipsed models are proposed depending upon the presence of α or β substituents.
9. An alternative to the Chautemps-Pierre model has apparently been described: Boeckman, R. K., Jr.; Thomas, E. W. J. Am. Chem. Soc. 1979, 101, 987.
10. Chamberlain, P.; Roberts, M. L.; Whitham, G. J. Chem. Soc. B 1970, 1374.
11. Kishi, Y. Aldrichimica Acta 1980, 13, 23.
12. Johnson, M. R.; Kishi, Y. Tetrahedron Lett. 1979, 4347.
13. Hasan, I.; Kishi, Y. Tetrahedron Lett. 1980, 4229.
14. See also: Narula, A. S. Tetrahedron Lett. 1981, 22, 2017.
15. 2 peroxidations: Sharpless, K. B.; Verhoeven, T. R. Aldrichimica Acta 1979, 18, 63.
16. 2 epoxidations like the perpendicular model, but with A = OH and attack occurring eclipsed to the OH group.
17. Schmid, G.; Fukuyama, T.; Akasaka, K.; Kishi, Y. J. Am. Chem. Soc. 1979, 101, 259.
18. Johnson, M. R.; Nakata, T.; Kishi, Y. Tetrahedron Lett. 1979, 4343.
19. Nagaoka, H.; Rutsch, W.; Schmid, G.; Iio, H.; Johnson, M. R.; Kishi, Y. J. Am. Chem. Soc. 1980, 102. 7962.
20. Toromanoff, E. Tetrahedron 1980, 36, 2809, follows changes in torsional angles for formation of products, which is in effect equivalent to an assumption of a productlike transition structure.
21. Caramella, P.; Rondan, N. G.; Paddon-Row, M. N.; Houk, K. N. J. Am. Chem. Soc. 1981, 103, 2438.
22. Rondan, N. G.; Paddon-Row, M. N.; Caramella, P.; Houk, K. N. J. Am. Chem. Soc. 1981, 103, 2436.
23. Baldwin, J. J. Chem. Soc., Chem. Commun. 1976, 734, 738.
24. Burgi, H. B.; Dunitz, J. D.; Lehn, J. M.; Wipff, G. Tetrahedron 1974, 30, 1563.
25. − attack), since there is a lower energy ion-molecule complex preceding this transition state. The predictions of conformations and barriers are excellent at even the minimal basis level in the absence of strongly polar bonds and adjacent lone pairs:
26. Pople, J. A. Tetrahedron 1974, 30, 1605.
27. −—Strozier, R. W.; Caramella, P.; Houk, K. N. J. Am. Chem. Soc. 1979, 101. 1340.
28. Nagase, S.; Kern, C. W. J. Am. Chem. Soc. 1979, 101, 2544.
29. Nagase, S.; Ray, N. K.; Morokuma, K. J. Am. Chem. Soc. 1980, 102, 4536.
30. Binkley, J. S.; Whiteside, R. A.; Krishnan, R.; Seeger, R.; DeFrees, D. J.; Schlegel, H. B.; Topiol, S.; Kahn, L. R.; Pople, J. A. Carnegie-Mellon University, Pittsburgh, PA.
31. This species was “manufactured” by the placement of a standard methyl on the STO-3G bridged ethyl cation (Williams, J. E.; Buss, V.; Allen, L. C.; Schleyer, P.V.R.; Latham, W. A.; Hehre, W. J.; Pople, J. A. J. Am. Chem. Soc. 1970, 92, 2141) and the optimization of the methyl rotational angle. Upon relaxation, this structure would collapse to the 2-propyl cation:
32. Radom, L.; Pople, J. A.; Buss, V.; Schleyer, P.V.R. J. Am. Chem. Soc 1972, 94, 311.
33. Scheiner, S.; Lipscomb, W. N.; Kleier, D. A. J. Am. Chem. Soc. 1976, 98, 4770.
34. Houk, K. N.; Strozier, R. W.; Rozeboom, M. D.; Nagase, S. J. Am. Chem. Soc. 1982, 104, 323.
35. Nagase, S.; Rondan, N. G.; Houk, K. N., unpublished results.
36. Rondan, N. G.; Houk, K. N.; Moss, R. A. J. Am. Chem. Soc. 1980, 102, 1770.
37. Klopman, G. In “Chemical Reactivity and Reaction Paths”; Klopman, G., Ed.; Wiley-Interscience: New York, 1974; Chapter 4, pp 55–166.
38. Houk, K. N. In “Frontiers of Free Radical Chemistry”; Pryor, W. A., Ed.; Academic Press: New York, 1980; pp 43–72.
39. Schowen, R. L.; Maggiora, G. M., unpublished results on acetaldehyde-water. The transition structures for the formaldehyde-water reaction have been published:
40. Williams, I. H.; Maggiora, G. M.; Schowen, R. L. J. Am. Chem. Soc. 1980, 102, 7831.
41. Williams, I. H.; Spangler, D.; Femec, D. A.; Maggiora, G. M.; Schowen, R. L. 1980, 102, 6619. These reactions have four-centered transition states, geometrically like the hydroboration reaction.
42. This factor has recently been proposed as the controlling factor in stereoselective nucleophilic additions to carbonyls: Cieplak, A. S. J. Am. Chem. Soc. 1981, 103, 4540.
43. Van Hemelrijk, D.; Van den Enden, L.; Giese, H. J.; Sellers, H. L.; Schafer, L. J. Am. Chem. Soc. 1980, 102, 2189.
44. − attack on formaldehyde has now been determined. The H---CO angle is 115°, and the transition structure is very near products: Eisenstein, O.; Schlegel, H. B.; Kayser, M. M. J. Org. Chem., 1982, 47, 2886.