Modeling Chemical Reactivity. 4. Regiochemistry and Stereochemistry of Electrophilic Additions to Allylic Double Bonds

Journal of the American Chemical Society

Volumn 109, Issue 3, 1987, Pages 650-663

  Kahn, S D ^a   Pau, C F ^a   Chamberlin, A R ^a   Hehre, W J ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 33845283500     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00237a003     Document Type: Article

References (40)

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10. (a) Pau, C. F.; Hehre, W. J. J. Comput. Chem., submitted. Hehre, W. J.; Pau, C. F.; Hout, R. F., Jr.; Francl, M. M. Molecular Modeling. Computer-Aided Descriptions of Molecular Structure and Reactivity; Wiley: New York, 1987.
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16. It has previously been noted that asymmetric substitution leads only to slight pyramidalization of the olefin. See: Houk, K. N. Methods Stereochem. Anal. 1983, 3, 1.
17. Hout, R. F., Jr.; Francl, M. M.; Kahn, S. D.; Dobbs, K. D.; Blurock, E. S.; Pietro, W. J.; McGrath, M. P.; Steckler, R.; Hehre, W. J. Quantum Chemistry Program Exchange; Indiana University: Bloomington, IN, to be submitted.
18. See: Francl, M. M.; Hout, R. F., Jr.; Hehre, W. J. J. Am. Chem. Soc. 1984, 106, 563.
19. The experimental energy difference between the ground-state CH eclipsed and CC eclipsed conformers of 1-butene is approximately 0.2 kcal mol-1, (a) Bothner-By, A. A.; Naar-Colin, C.; Gunther, H. J. Am. Chem. Soc. 1962, 84, 2748. Bothner-By, A. A.; Gunther, H. Discuss. Faraday Soc. 1962, 34, 127. Kondo, S.; Hirota, E.; Morino, Y. J. Mol. Spectrosc. 1968, 28, 471.
20. (a) Imachi, M.; Nakagawa, J.; Hayashi, M. J. Mol. Struct. 1983, 102, 403. An earlier report from the same group suggested a dihedral angle of 103.5° [ Hayashi, M.; Imachi, M.; Saito, M. Chem. Lett. 1977, 221], closer to the value of 102 ± 1° obtained by electron diffraction [ Beagley, B.; Foord, A.; Moutran, R; Roszondai, R. J. Mol. Struct. 1977, 117]. The results of an infrared and Raman study show a C=CCSi dihedral angle of between 90 and 120°: (d) Ohno, K.; Toga, K.; Murata, H. Bull. Chem. Soc. Jpn. 1977, 50, 2870.
21. This is commonly known as the “β-silyl” effect. for experimental support, see: Wiedner, U.; Schweig, A. Angew. Chem., Int. Ed. Engl. 1972, 11, 146.
22. Smith, Z.; Carballo, N.; Wilson. E. B.; Marstokk, K. M. ; Mollendal, J. J. Am. Chem. Soc. 1985, 107, 1951.
23. Part 6: Kahn, S. D.; Hehre, W. J. J. Am. Chem. Soc., following in this issue.
24. (a) Bothner-By, A. A.; Castellano, S.; Ebersole, S. J.; Gunther, H. J. Am. Chem. Soc. 1966, 88, 2466. Tronchet, J. M. H.; Xuan. T. N. Carbohydr. Res. 1978, 67, 469. Lessard, J.; Saunders, J. K.; Viet, M. T. P. Tetrahedron Lett. 1982, 23, 2059. (d) Gonnella, N. C.; Nakanishi, K.; Martin, V. S.; Sharpless, K. B. J. Am. Chem. Soc. 1982, 104, 3775. See also: (e) Stork, G.; Kahn, M. Tetrahedron Lett. 1983. 24, 3951.
25. (a) Giese, B.; Bartman, D. Tetrahedron Lett. 1985, 26, 1197. Chamberlin, A. R.; Mulholland, R. L., Jr. Tetrahedron 1984, 40, 2297. Cha, J. K.; Christ, W. J.; Kishi, Y. J. Am. Chem. Soc. 1984, 40, 2247. (d) Chamberlin, A. R.; Dezube, M.; Dussault, P.; McMills, M. C. J. Am. Chem. Soc. 1983, 105, 5819. (e) Still, W. C.; Barrish, J. C. J. Am. Chem. Soc. 1983, 105, 2487. (f) Rossiter, B. E.; Verhoeven, T. R.; Sharpless, K. B. Tetrahedron Lett. 1979, 4733. (g) Raiter, M.; Castaing, M.; Godet, J.; Peryre, M. J. Chem. Res. (S) 1978, 179. (h) Bellucci, G.; Bianchini, R.; Ingrosso, G.; Mastrorilli, E. Gazz. Chim. Ital. 1978, 108, 643. (i) Chantemps, P.; Pierre, J. L. Tetrahedron 1976, 32, 549. (j) Tanaka, S.; Yamamoto, H.; Nozaki, H.; Sharpless, K. B.; Michaelson, R. C.; Cutting, J. D. J. Am. Chem. Soc. 1974, 96, 5254. (k) Chamberlain, P.; Whitham, G. H. J. Chem. Soc. 1970, 1382.
26. (a) Similar reasoning has been used to rationalize variances in π-ionization energies in allyl alcohol and several cyclic allylic alcohols. See: Brown, R. S.; Marcinko, R. W. J. Am. Chem. Soc. 1978, 100, 5721. for a discussion of the conformational preferences, and their causes, in allyl alchol, see: Aspiala, A.; Lotta, T.; Murto, J.; Rasanen, M. J. Chem. Phys. 1983, 79, 4183. Kao, J.; Katz, T. J. Mol. Struct. 1984, 108, 229.
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29. For recent reviews, see: (a) Scrocco, E.; Tomasi, J. Adv. Quantum Chem. 1978. 11, 115. Chemical Applications of Atomic and molecular Electrostatic Potentials, Politzer, P., Truhlar, D. G., Eds.; Plenum: New York. 1981.
30. The relative importance of CH and CC hyperconjugation has not been clearly resolved in the literature. for a recent discussion, see: Sunko, D. E.; Hehre, W. J. Prog. Phys. Org. Chem. 1983, 14, 205 and references therein.
31. Kahn, S. D.; Chamberlin, A. R.; Hehre, W. J., research in progress.
32. Barili, P. L.; Bellucci, G.; Marioni, F.; Morelli, I.; Scartoni, V. J. Org. Chem. 1972, 37, 4353.
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34. For example, see: Lance, D. G.; Szarek, W. A.; Jones, J. K. N.; Howarth, G. B. Can. J. Chem. 1969, 47, 2871.
35. For references to the mechanism of cis hydroxylation with OsO4and KMnO4, see: Schroder, M. Chem. Rev. 1980, 80, 187.
36. Part 7: Chamberlin, A. R.; Mulholland, R. L., Jr.; Kahn, S. D.; Hehre, W. J. J. Am. Chem. Soc., in this issue.
37. Part 7: Chamberlin, A. R.; Mulholland, R. L., Jr.; Kahn, S. D.; Hehre, W. J. J. Am. Chem. Soc., in this issue.
38. This has previously been noted. See: Chan, T. H.; Fleming, I. Synthesis 1979, 761.
39. This follows from simple perturbation molecular orbital theory. for discussions, see ref 12c and the following: (a) Chemical Reactivity and Reaction Paths, Klopman, G., Ed.; Wiley: New York, 1984. Dewer, M. J. S.; Dougherty, R. C. The PMO Theory of Organic Chemistry; Plenum: New York, 1985.
40. For pictorial representations of molecular orbitals, sec: (a) Jorgensen, W. L.; Salem, L. The Organic Chemists Book of Orbitals; Academic: New York, 1970. Hout, R. F., Jr.; Pietro, W. J.; Hehre, W. J. A Pictorial Approach to Molecular Structure and Reactivity; Wiley: New York, 1984.