Stereodependence of the Effect of α Substituants on the Face Reactivity of Conformationally Rigid Ketones toward Metal Hydrides. Is There an Antiperiplanar (Cieplak) Effect?

Journal of Organic Chemistry

Volumn 62, Issue 18, 1997, Pages 6164-6176

  Fraser, Robert R ^a   Faibish, Neil C ^a   Kong, Fanzuo ^a,b   Bednarski, Krzysztof ^a  

^a UNIVERSITY OF OTTAWA   (Canada)

^b RESEARCH CENTER FOR ECO ENVIRONMENTAL SCIENCES   (China)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001690892     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo970428p     Document Type: Article

References (84)

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17. For an alternative consideration of electrostatic effects using a frontier molecular orbital approach, see: Huang, X. L.; Dannenberg, J. J. J. Am. Chem. Soc. 1993, 115, 4025, 6017.
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22. Gung, B. W. Tetrahedron 1996, 52, 5263. Space limitations preclude a complete listing of references. For a more exhaustive coverage of the literature, see also the recent references 12, 13, and 16.
23. It is noteworthy that interpretation of inductive effects of β and γ substituents on face selectivity is inherently ambiguous. The majority of face selectivity measurements will be qualitatively consistent with either explanation. Arguments for or against electrostatic effects must entail assumptions regarding the orientation of the bond dipoles in a transition state for which mechanistic evidence is scant and qualitative (vide infra).
24. These include (a) additions to alkenes [Lau, J.; Gonikberg, E. M.; Hung, J.; le Noble, W. J. J. Am. Chem. Soc. 1995, 117, 11421. Bellucci, G.; Chiappe, C.; Moro, G. L.; Ingrosso, G. J. Org. Chem. 1995, 60, 6214, Jones, G. R.; Vogel, P.; J. Chem. Soc., Chem. Commun. 1993, 769], (b) photoadditions [Lau, J.; Gonikberg, E. M.; Hung, J.; le Noble, W. J. J. Am. Chem. Soc. 1995, 117, 11421. Coxon, J. M.; McDonald, D. Q. Tetrahedron Lett. 1992, 33, 6511, (c) radical capture [Bodepudi, V. R.; le Noble, W. J. J. Org. Chem. 1991, 56, 2001], (d) nucleophilic addition to carbocations [Song, I. H.; le Noble, W. J. J. Org. Chem. 1994, 59, 58], (e) sulfur oxidation [Mukherjee, A. K.; le Noble, W. J. J. Org. Chem. 1993, 50, 7955], and (f) sigmatropic rearrangements [Lau, J.; Gonikberg, E. M.; Hung, J.; le Noble, W. J. J. Am. Chem. Soc. 1995, 117, 11421].
25. These include (a) additions to alkenes [Lau, J.; Gonikberg, E. M.; Hung, J.; le Noble, W. J. J. Am. Chem. Soc. 1995, 117, 11421. Bellucci, G.; Chiappe, C.; Moro, G. L.; Ingrosso, G. J. Org. Chem. 1995, 60, 6214, Jones, G. R.; Vogel, P.; J. Chem. Soc., Chem. Commun. 1993, 769], (b) photoadditions [Lau, J.; Gonikberg, E. M.; Hung, J.; le Noble, W. J. J. Am. Chem. Soc. 1995, 117, 11421. Coxon, J. M.; McDonald, D. Q. Tetrahedron Lett. 1992, 33, 6511, (c) radical capture [Bodepudi, V. R.; le Noble, W. J. J. Org. Chem. 1991, 56, 2001], (d) nucleophilic addition to carbocations [Song, I. H.; le Noble, W. J. J. Org. Chem. 1994, 59, 58], (e) sulfur oxidation [Mukherjee, A. K.; le Noble, W. J. J. Org. Chem. 1993, 50, 7955], and (f) sigmatropic rearrangements [Lau, J.; Gonikberg, E. M.; Hung, J.; le Noble, W. J. J. Am. Chem. Soc. 1995, 117, 11421].
26. These include (a) additions to alkenes [Lau, J.; Gonikberg, E. M.; Hung, J.; le Noble, W. J. J. Am. Chem. Soc. 1995, 117, 11421. Bellucci, G.; Chiappe, C.; Moro, G. L.; Ingrosso, G. J. Org. Chem. 1995, 60, 6214, Jones, G. R.; Vogel, P.; J. Chem. Soc., Chem. Commun. 1993, 769], (b) photoadditions [Lau, J.; Gonikberg, E. M.; Hung, J.; le Noble, W. J. J. Am. Chem. Soc. 1995, 117, 11421. Coxon, J. M.; McDonald, D. Q. Tetrahedron Lett. 1992, 33, 6511, (c) radical capture [Bodepudi, V. R.; le Noble, W. J. J. Org. Chem. 1991, 56, 2001], (d) nucleophilic addition to carbocations [Song, I. H.; le Noble, W. J. J. Org. Chem. 1994, 59, 58], (e) sulfur oxidation [Mukherjee, A. K.; le Noble, W. J. J. Org. Chem. 1993, 50, 7955], and (f) sigmatropic rearrangements [Lau, J.; Gonikberg, E. M.; Hung, J.; le Noble, W. J. J. Am. Chem. Soc. 1995, 117, 11421].
27. These include (a) additions to alkenes [Lau, J.; Gonikberg, E. M.; Hung, J.; le Noble, W. J. J. Am. Chem. Soc. 1995, 117, 11421. Bellucci, G.; Chiappe, C.; Moro, G. L.; Ingrosso, G. J. Org. Chem. 1995, 60, 6214, Jones, G. R.; Vogel, P.; J. Chem. Soc., Chem. Commun. 1993, 769], (b) photoadditions [Lau, J.; Gonikberg, E. M.; Hung, J.; le Noble, W. J. J. Am. Chem. Soc. 1995, 117, 11421. Coxon, J. M.; McDonald, D. Q. Tetrahedron Lett. 1992, 33, 6511, (c) radical capture [Bodepudi, V. R.; le Noble, W. J. J. Org. Chem. 1991, 56, 2001], (d) nucleophilic addition to carbocations [Song, I. H.; le Noble, W. J. J. Org. Chem. 1994, 59, 58], (e) sulfur oxidation [Mukherjee, A. K.; le Noble, W. J. J. Org. Chem. 1993, 50, 7955], and (f) sigmatropic rearrangements [Lau, J.; Gonikberg, E. M.; Hung, J.; le Noble, W. J. J. Am. Chem. Soc. 1995, 117, 11421].
28. These include (a) additions to alkenes [Lau, J.; Gonikberg, E. M.; Hung, J.; le Noble, W. J. J. Am. Chem. Soc. 1995, 117, 11421. Bellucci, G.; Chiappe, C.; Moro, G. L.; Ingrosso, G. J. Org. Chem. 1995, 60, 6214, Jones, G. R.; Vogel, P.; J. Chem. Soc., Chem. Commun. 1993, 769], (b) photoadditions [Lau, J.; Gonikberg, E. M.; Hung, J.; le Noble, W. J. J. Am. Chem. Soc. 1995, 117, 11421. Coxon, J. M.; McDonald, D. Q. Tetrahedron Lett. 1992, 33, 6511, (c) radical capture [Bodepudi, V. R.; le Noble, W. J. J. Org. Chem. 1991, 56, 2001], (d) nucleophilic addition to carbocations [Song, I. H.; le Noble, W. J. J. Org. Chem. 1994, 59, 58], (e) sulfur oxidation [Mukherjee, A. K.; le Noble, W. J. J. Org. Chem. 1993, 50, 7955], and (f) sigmatropic rearrangements [Lau, J.; Gonikberg, E. M.; Hung, J.; le Noble, W. J. J. Am. Chem. Soc. 1995, 117, 11421].
29. These include (a) additions to alkenes [Lau, J.; Gonikberg, E. M.; Hung, J.; le Noble, W. J. J. Am. Chem. Soc. 1995, 117, 11421. Bellucci, G.; Chiappe, C.; Moro, G. L.; Ingrosso, G. J. Org. Chem. 1995, 60, 6214, Jones, G. R.; Vogel, P.; J. Chem. Soc., Chem. Commun. 1993, 769], (b) photoadditions [Lau, J.; Gonikberg, E. M.; Hung, J.; le Noble, W. J. J. Am. Chem. Soc. 1995, 117, 11421. Coxon, J. M.; McDonald, D. Q. Tetrahedron Lett. 1992, 33, 6511, (c) radical capture [Bodepudi, V. R.; le Noble, W. J. J. Org. Chem. 1991, 56, 2001], (d) nucleophilic addition to carbocations [Song, I. H.; le Noble, W. J. J. Org. Chem. 1994, 59, 58], (e) sulfur oxidation [Mukherjee, A. K.; le Noble, W. J. J. Org. Chem. 1993, 50, 7955], and (f) sigmatropic rearrangements [Lau, J.; Gonikberg, E. M.; Hung, J.; le Noble, W. J. J. Am. Chem. Soc. 1995, 117, 11421].
30. These include (a) additions to alkenes [Lau, J.; Gonikberg, E. M.; Hung, J.; le Noble, W. J. J. Am. Chem. Soc. 1995, 117, 11421. Bellucci, G.; Chiappe, C.; Moro, G. L.; Ingrosso, G. J. Org. Chem. 1995, 60, 6214, Jones, G. R.; Vogel, P.; J. Chem. Soc., Chem. Commun. 1993, 769], (b) photoadditions [Lau, J.; Gonikberg, E. M.; Hung, J.; le Noble, W. J. J. Am. Chem. Soc. 1995, 117, 11421. Coxon, J. M.; McDonald, D. Q. Tetrahedron Lett. 1992, 33, 6511, (c) radical capture [Bodepudi, V. R.; le Noble, W. J. J. Org. Chem. 1991, 56, 2001], (d) nucleophilic addition to carbocations [Song, I. H.; le Noble, W. J. J. Org. Chem. 1994, 59, 58], (e) sulfur oxidation [Mukherjee, A. K.; le Noble, W. J. J. Org. Chem. 1993, 50, 7955], and (f) sigmatropic rearrangements [Lau, J.; Gonikberg, E. M.; Hung, J.; le Noble, W. J. J. Am. Chem. Soc. 1995, 117, 11421].
31. These include (a) additions to alkenes [Lau, J.; Gonikberg, E. M.; Hung, J.; le Noble, W. J. J. Am. Chem. Soc. 1995, 117, 11421. Bellucci, G.; Chiappe, C.; Moro, G. L.; Ingrosso, G. J. Org. Chem. 1995, 60, 6214, Jones, G. R.; Vogel, P.; J. Chem. Soc., Chem. Commun. 1993, 769], (b) photoadditions [Lau, J.; Gonikberg, E. M.; Hung, J.; le Noble, W. J. J. Am. Chem. Soc. 1995, 117, 11421. Coxon, J. M.; McDonald, D. Q. Tetrahedron Lett. 1992, 33, 6511, (c) radical capture [Bodepudi, V. R.; le Noble, W. J. J. Org. Chem. 1991, 56, 2001], (d) nucleophilic addition to carbocations [Song, I. H.; le Noble, W. J. J. Org. Chem. 1994, 59, 58], (e) sulfur oxidation [Mukherjee, A. K.; le Noble, W. J. J. Org. Chem. 1993, 50, 7955], and (f) sigmatropic rearrangements [Lau, J.; Gonikberg, E. M.; Hung, J.; le Noble, W. J. J. Am. Chem. Soc. 1995, 117, 11421].
32. These include (a) additions to alkenes [Lau, J.; Gonikberg, E. M.; Hung, J.; le Noble, W. J. J. Am. Chem. Soc. 1995, 117, 11421. Bellucci, G.; Chiappe, C.; Moro, G. L.; Ingrosso, G. J. Org. Chem. 1995, 60, 6214, Jones, G. R.; Vogel, P.; J. Chem. Soc., Chem. Commun. 1993, 769], (b) photoadditions [Lau, J.; Gonikberg, E. M.; Hung, J.; le Noble, W. J. J. Am. Chem. Soc. 1995, 117, 11421. Coxon, J. M.; McDonald, D. Q. Tetrahedron Lett. 1992, 33, 6511, (c) radical capture [Bodepudi, V. R.; le Noble, W. J. J. Org. Chem. 1991, 56, 2001], (d) nucleophilic addition to carbocations [Song, I. H.; le Noble, W. J. J. Org. Chem. 1994, 59, 58], (e) sulfur oxidation [Mukherjee, A. K.; le Noble, W. J. J. Org. Chem. 1993, 50, 7955], and (f) sigmatropic rearrangements [Lau, J.; Gonikberg, E. M.; Hung, J.; le Noble, W. J. J. Am. Chem. Soc. 1995, 117, 11421].
33. Eliel, E. L.; Senda, Y. Tetrahedron 1970, 26, 2411.
34. Rickborn, B.; Wuesthoff, M. T. J. Am. Chem. Soc. 1970, 92, 6894.
35. Wigfield, D. C.; Phelps, D. J. J. Am. Chem. Soc. 1974, 96, 543.
36. Senda, Y.; Nakano, S.; Kunii, H.; Itoh, H. J. Chem. Soc., Perkin Trans. 2 1993, 1009.
37. 17 these relative rate measurements were made on reactions involving consumption of all 4 equiv of hydride by 1 equiv of a pair of ketones.
38. Mislow, K.; Glass, M. A. W.; O'Brien, R. E.; Rutkin, P.; Steinberg, D. H.; Weiss, J.; Djerassi, C. J. Am. Chem. Soc. 1962, 84, 1455. The structure of 1 is shown in Figure 2.
39. (a) Fraser, R. R.; Champagne, P. J. Can. J. Chem. 1976, 54, 3809.
40. (b) Fraser, R. R.; Stanciulesçu, M. J. Am. Chem. Soc. 1987, 109, 1580.
41. (c) Fraser, R. R.; Kong, F.; Stanciulesçu, M.; Wu, Y.-D.; Houk, K. N. J. Org. Chem. 1993, 58, 4431.
42. 25
43. (a) Fraser, R. R.; Bensimon, C.; Kong, F.; Wu, X. Can. J. Chem. 1993, 71, 685.
44. (b) Fraser, R. R.; Bensimon, C.; Faibish, N. C.; Kong, F. Can. J. Chem. 1994, 72, 1481.
45. 27 revealed the fluoro substituent to have the strongest preference for the equatorial position in that system as well.
46. Fraser, R. R.; Faibish, N. C. Can. J. Chem. 1995, 73, 88.
47. Boone, J. R.; Ashby, E. C. Top. Stereochem. 1979, 11, 53.
48. (a) Brown, H. C.; McFarlin, R. F. J. Am. Chem. Soc. 1958, 80, 5372.
49. (b) Brown, H. C.; Shoaf, C. J. J. Am. Chem. Soc. 1964, 86, 1079.
50. Ashby, E. C.; Boone, J. R. J. Am. Chem. Soc. 1976, 98, 5524.
51. Wiegers, K. E.; Smith, S. G. J. Org. Chem. 1978, 43, 1126.
52. Wiegers, K. E.; Smith, S. G. J. Am. Chem. Soc. 1977, 99, 1480. See also: Brown, H. C.; Deck, H. R. J. Am. Chem. Soc. 1965, 87, 5620.
53. Wiegers, K. E.; Smith, S. G. J. Am. Chem. Soc. 1977, 99, 1480. See also: Brown, H. C.; Deck, H. R. J. Am. Chem. Soc. 1965, 87, 5620.
54. - as the reducing agent.
55. The assignment of stereochemistry to each pair of diastereomeric alcohols is based on the magnitude of the vicinal coupling constants between the protons at C5 and C6. The proton spectrum of the major alcohol 13 typically lacks a large vicinal splitting (for the dihedral angle of 160°) as a consequence of hydride addition app to the axial substituent. The spectrum for the major alcohol resulting from addition ac to the equatorial substituent is identifiable by its lack of the very small splitting (<2 Hz) associated with an 80° dihedral 4 angle. Figures 4b and 4c depict these stereochemical arrangements.
56. WigfieId, D. C. Tetrahedron 1979, 35, 449.
57. The consumption of hydride has been minimized to restrict epimerization and the rearrangement of the substituted ketone both of which increase as the reaction progresses.
58. 3·ether, we found that the reduction of 1 was remarkably free from any side products when run in acetonitrile.
59. Doyle, M. P.; West, C. T.; Donnelly, S. J.; McOsker, C. C. J. Organomet. Chem. 1976, 117, 129.
60. In one instance reduction of the axial methoxyl was accompanied by a product of rearrangement and reduction, for which a correction in the calculated rate ratio was made.
61. For a comprehensive list of review articles, see: Lowry, T. H.; Richardson, K. S. Mechanism and Theory in Organic Chemistry, 3rd ed., Harper and Row: New York, 1987; p 143, ref 28. See also: Taft, R. W., Jr. In Steric Effects in Organic Chemistry; Newman, M. S., Ed.; John Wiley & Sons: New York, 1956; pp 607-610.
62. For a comprehensive list of review articles, see: Lowry, T. H.; Richardson, K. S. Mechanism and Theory in Organic Chemistry, 3rd ed., Harper and Row: New York, 1987; p 143, ref 28. See also: Taft, R. W., Jr. In Steric Effects in Organic Chemistry; Newman, M. S., Ed.; John Wiley & Sons: New York, 1956; pp 607-610.
63. (a) Taft, R. W., Jr. J. Am. Chem. Soc. 1952, 74, 3120.
64. (b) Taft, R. W., Jr. J. Am. Chem. Soc. 1953, 75, 4231.
65. I(F) = 0.56 (as cited by Charton, M. Prog. Phys. Org. Chem. 1981, 13, 119-251, p 171), as they proved to provide excellent correlations in reactions involving addition of pinacolone lithium enolate to α-substituted ketones; Das, G.; Thornton, E. R. J. Am. Chem. Soc. 1993, 115, 1302.
66. I(F) = 0.56 (as cited by Charton, M. Prog. Phys. Org. Chem. 1981, 13, 119-251, p 171), as they proved to provide excellent correlations in reactions involving addition of pinacolone lithium enolate to α-substituted ketones; Das, G.; Thornton, E. R. J. Am. Chem. Soc. 1993, 115, 1302.
67. Solvent effects on ρ can be expected to resemble those reported for Hammett plots, ref 40, p 146.
68. 41c p 606.
69. The Lewis acid coordinated to the ketone in a and c is expected to lie in the nodal plane of the π bond of the carbonyl as established by X-ray for a methylaluminum diaryloxide complex of benzophenone; Power, M. B.; Bott, S. G.; Atwood, J. L.; Barron, A. R. J. Am. Chem. Soc. 1990, 112, 3446.
70. Field effect contributions and limitations to the success of Taft correlations are discussed in Hine, J. Structural Effects on Equilibria in Organic Chemistry; Wiley-Interscience: New York, 1975; pp 32-37 and 92-95.
71. I value of -0.06 for a methyl substituent is considered negligible.
72. Anh's calculations predicted the app methyl and chloro groups to provide 1.9 and 23.5 kcal/mol of stabilization, respectively. Because Cieplak has proposed their effects to be destabilizing, all reactivities found to be in accord with his theory will be in opposition to Anh's and vice versa.
73. 7 in interpreting their data in terms of an orbital interaction is not justified, as discussed below.
74. 51
75. (a) Reynolds, W. F. J. Chem. Soc. Perkin Trans. 2 1980, 985.
76. (b) Bowden, K.; Grubbs, E. J. Prog. Phys. Org. Chem. 1993, 19, 183.
77. 2,46 The accuracy of either method is limited by the estimate of charge distribution in the transition state, as well as the uncertainty of the value selected for the dielectric constant of the medium.
78. In the parent ketones 6 and 8, the two conformations with the methyl group gauche to the vicinal hydrogen have the same stability, with the third conformation being more than 3 kcal/mol higher in energy as calculated using the MMX program PCMODEL.
79. 46,51
80. 3-catalyzed reductions rules out chelation as having important influence on relative rates.
81. Scholz, D. Synthesis 1983, 944.
82. The author has deposited the atomic coordinates for the structures 8 and 11 with the Cambridge Crystallographic Data Center. The coordinates can be obtained, on request, from the Director, Cambridge Crystallographic Data Center, 12 Union Road, Cambridge, CB2 1EZ, U.K.
83. Differding, E.; Ofner, H. Synlett 1991, 187.
84. Lyttle, D. A.; Jensen, E. H.; Struck, W. A. Anal. Chem. 1952, 24, 1843.