Conformational analysis and the transition state in asymmetric reductions with boranes based on (+)-α-pinene. 1. Benzaldehyde reduction with alpine borane and other B-alkyl-9-borabicyclo[3.3.1]nonanes. A semiempirical study

Journal of Organic Chemistry

Volumn 61, Issue 4, 1996, Pages 1341-1345

  Rogic, Milorad M ^a,b  

^a Molec Modeling Research Institute   (United States)

^b NONE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001431355     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9520046     Document Type: Article

References (53)

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17. 6f-h investigated stereoselectivities of the reductions of ketones and conformational analysis of chiral alkenes and oxonium ions using ab initio calculations; they developed an improved MM2 force field which qualitatively reproduces observed stereoselectivities: (a) Jones, D. K.; Liotta, D. C.; Shinkai, I.; Mathre, D. J. J. Org. Chem. 1993, 58, 799. (b) Houk. K. N.; Rondan, N. G.; Wu, Y. D.; Metz, J. T.; Paddon-Row, M. N. Tetrahedron 1984, 40, 2257. (c) Houk, K. N.; Paddon-Row, M. N.; Rondan, N. G.; Wu, Y. D.; Brown, F. K.; Spellmeyer, D. C.; Metz, J. T.; Li, Y.; Loncharich, R. J. Science 1986, 231, 1108. (d) Masamune, S.; Kennedy, R. M.; Petersen, J. S.; Houk, K. N.; Wu, Y. D. J. Am. Chem. Soc. 1986, 108, 1986. (e) Eksterowez, J. E.; Houk, K. N. Chem. Rev. 1993, 93, 2439. (f) Wu, Y.-D.; Houk, K. N., Florez, J.; Trost. B M. J. Org. Chem. 1991, 56, 3656. (g) Wu, Y.-D.; Tucker, J. A.; Houk, K. N. J. Am. Chem. Soc. 1991, 113, 5018. (h) Broeker, J. L.; Hoffmann, R. W.; Houk, K. N. J. Am. Chem. Soc. 1991, 113, 5006.
18. 6f-h investigated stereoselectivities of the reductions of ketones and conformational analysis of chiral alkenes and oxonium ions using ab initio calculations; they developed an improved MM2 force field which qualitatively reproduces observed stereoselectivities: (a) Jones, D. K.; Liotta, D. C.; Shinkai, I.; Mathre, D. J. J. Org. Chem. 1993, 58, 799. (b) Houk. K. N.; Rondan, N. G.; Wu, Y. D.; Metz, J. T.; Paddon-Row, M. N. Tetrahedron 1984, 40, 2257. (c) Houk, K. N.; Paddon-Row, M. N.; Rondan, N. G.; Wu, Y. D.; Brown, F. K.; Spellmeyer, D. C.; Metz, J. T.; Li, Y.; Loncharich, R. J. Science 1986, 231, 1108. (d) Masamune, S.; Kennedy, R. M.; Petersen, J. S.; Houk, K. N.; Wu, Y. D. J. Am. Chem. Soc. 1986, 108, 1986. (e) Eksterowez, J. E.; Houk, K. N. Chem. Rev. 1993, 93, 2439. (f) Wu, Y.-D.; Houk, K. N., Florez, J.; Trost. B M. J. Org. Chem. 1991, 56, 3656. (g) Wu, Y.-D.; Tucker, J. A.; Houk, K. N. J. Am. Chem. Soc. 1991, 113, 5018. (h) Broeker, J. L.; Hoffmann, R. W.; Houk, K. N. J. Am. Chem. Soc. 1991, 113, 5006.
19. 6f-h investigated stereoselectivities of the reductions of ketones and conformational analysis of chiral alkenes and oxonium ions using ab initio calculations; they developed an improved MM2 force field which qualitatively reproduces observed stereoselectivities: (a) Jones, D. K.; Liotta, D. C.; Shinkai, I.; Mathre, D. J. J. Org. Chem. 1993, 58, 799. (b) Houk. K. N.; Rondan, N. G.; Wu, Y. D.; Metz, J. T.; Paddon-Row, M. N. Tetrahedron 1984, 40, 2257. (c) Houk, K. N.; Paddon-Row, M. N.; Rondan, N. G.; Wu, Y. D.; Brown, F. K.; Spellmeyer, D. C.; Metz, J. T.; Li, Y.; Loncharich, R. J. Science 1986, 231, 1108. (d) Masamune, S.; Kennedy, R. M.; Petersen, J. S.; Houk, K. N.; Wu, Y. D. J. Am. Chem. Soc. 1986, 108, 1986. (e) Eksterowez, J. E.; Houk, K. N. Chem. Rev. 1993, 93, 2439. (f) Wu, Y.-D.; Houk, K. N., Florez, J.; Trost. B M. J. Org. Chem. 1991, 56, 3656. (g) Wu, Y.-D.; Tucker, J. A.; Houk, K. N. J. Am. Chem. Soc. 1991, 113, 5018. (h) Broeker, J. L.; Hoffmann, R. W.; Houk, K. N. J. Am. Chem. Soc. 1991, 113, 5006.
20. 6f-h investigated stereoselectivities of the reductions of ketones and conformational analysis of chiral alkenes and oxonium ions using ab initio calculations; they developed an improved MM2 force field which qualitatively reproduces observed stereoselectivities: (a) Jones, D. K.; Liotta, D. C.; Shinkai, I.; Mathre, D. J. J. Org. Chem. 1993, 58, 799. (b) Houk. K. N.; Rondan, N. G.; Wu, Y. D.; Metz, J. T.; Paddon-Row, M. N. Tetrahedron 1984, 40, 2257. (c) Houk, K. N.; Paddon-Row, M. N.; Rondan, N. G.; Wu, Y. D.; Brown, F. K.; Spellmeyer, D. C.; Metz, J. T.; Li, Y.; Loncharich, R. J. Science 1986, 231, 1108. (d) Masamune, S.; Kennedy, R. M.; Petersen, J. S.; Houk, K. N.; Wu, Y. D. J. Am. Chem. Soc. 1986, 108, 1986. (e) Eksterowez, J. E.; Houk, K. N. Chem. Rev. 1993, 93, 2439. (f) Wu, Y.-D.; Houk, K. N., Florez, J.; Trost. B M. J. Org. Chem. 1991, 56, 3656. (g) Wu, Y.-D.; Tucker, J. A.; Houk, K. N. J. Am. Chem. Soc. 1991, 113, 5018. (h) Broeker, J. L.; Hoffmann, R. W.; Houk, K. N. J. Am. Chem. Soc. 1991, 113, 5006.
21. 6f-h investigated stereoselectivities of the reductions of ketones and conformational analysis of chiral alkenes and oxonium ions using ab initio calculations; they developed an improved MM2 force field which qualitatively reproduces observed stereoselectivities: (a) Jones, D. K.; Liotta, D. C.; Shinkai, I.; Mathre, D. J. J. Org. Chem. 1993, 58, 799. (b) Houk. K. N.; Rondan, N. G.; Wu, Y. D.; Metz, J. T.; Paddon-Row, M. N. Tetrahedron 1984, 40, 2257. (c) Houk, K. N.; Paddon-Row, M. N.; Rondan, N. G.; Wu, Y. D.; Brown, F. K.; Spellmeyer, D. C.; Metz, J. T.; Li, Y.; Loncharich, R. J. Science 1986, 231, 1108. (d) Masamune, S.; Kennedy, R. M.; Petersen, J. S.; Houk, K. N.; Wu, Y. D. J. Am. Chem. Soc. 1986, 108, 1986. (e) Eksterowez, J. E.; Houk, K. N. Chem. Rev. 1993, 93, 2439. (f) Wu, Y.-D.; Houk, K. N., Florez, J.; Trost. B M. J. Org. Chem. 1991, 56, 3656. (g) Wu, Y.-D.; Tucker, J. A.; Houk, K. N. J. Am. Chem. Soc. 1991, 113, 5018. (h) Broeker, J. L.; Hoffmann, R. W.; Houk, K. N. J. Am. Chem. Soc. 1991, 113, 5006.
22. 6f-h investigated stereoselectivities of the reductions of ketones and conformational analysis of chiral alkenes and oxonium ions using ab initio calculations; they developed an improved MM2 force field which qualitatively reproduces observed stereoselectivities: (a) Jones, D. K.; Liotta, D. C.; Shinkai, I.; Mathre, D. J. J. Org. Chem. 1993, 58, 799. (b) Houk. K. N.; Rondan, N. G.; Wu, Y. D.; Metz, J. T.; Paddon-Row, M. N. Tetrahedron 1984, 40, 2257. (c) Houk, K. N.; Paddon-Row, M. N.; Rondan, N. G.; Wu, Y. D.; Brown, F. K.; Spellmeyer, D. C.; Metz, J. T.; Li, Y.; Loncharich, R. J. Science 1986, 231, 1108. (d) Masamune, S.; Kennedy, R. M.; Petersen, J. S.; Houk, K. N.; Wu, Y. D. J. Am. Chem. Soc. 1986, 108, 1986. (e) Eksterowez, J. E.; Houk, K. N. Chem. Rev. 1993, 93, 2439. (f) Wu, Y.-D.; Houk, K. N., Florez, J.; Trost. B M. J. Org. Chem. 1991, 56, 3656. (g) Wu, Y.-D.; Tucker, J. A.; Houk, K. N. J. Am. Chem. Soc. 1991, 113, 5018. (h) Broeker, J. L.; Hoffmann, R. W.; Houk, K. N. J. Am. Chem. Soc. 1991, 113, 5006.
23. 6f-h investigated stereoselectivities of the reductions of ketones and conformational analysis of chiral alkenes and oxonium ions using ab initio calculations; they developed an improved MM2 force field which qualitatively reproduces observed stereoselectivities: (a) Jones, D. K.; Liotta, D. C.; Shinkai, I.; Mathre, D. J. J. Org. Chem. 1993, 58, 799. (b) Houk. K. N.; Rondan, N. G.; Wu, Y. D.; Metz, J. T.; Paddon-Row, M. N. Tetrahedron 1984, 40, 2257. (c) Houk, K. N.; Paddon-Row, M. N.; Rondan, N. G.; Wu, Y. D.; Brown, F. K.; Spellmeyer, D. C.; Metz, J. T.; Li, Y.; Loncharich, R. J. Science 1986, 231, 1108. (d) Masamune, S.; Kennedy, R. M.; Petersen, J. S.; Houk, K. N.; Wu, Y. D. J. Am. Chem. Soc. 1986, 108, 1986. (e) Eksterowez, J. E.; Houk, K. N. Chem. Rev. 1993, 93, 2439. (f) Wu, Y.-D.; Houk, K. N., Florez, J.; Trost. B M. J. Org. Chem. 1991, 56, 3656. (g) Wu, Y.-D.; Tucker, J. A.; Houk, K. N. J. Am. Chem. Soc. 1991, 113, 5018. (h) Broeker, J. L.; Hoffmann, R. W.; Houk, K. N. J. Am. Chem. Soc. 1991, 113, 5006.
24. 6f-h investigated stereoselectivities of the reductions of ketones and conformational analysis of chiral alkenes and oxonium ions using ab initio calculations; they developed an improved MM2 force field which qualitatively reproduces observed stereoselectivities: (a) Jones, D. K.; Liotta, D. C.; Shinkai, I.; Mathre, D. J. J. Org. Chem. 1993, 58, 799. (b) Houk. K. N.; Rondan, N. G.; Wu, Y. D.; Metz, J. T.; Paddon-Row, M. N. Tetrahedron 1984, 40, 2257. (c) Houk, K. N.; Paddon-Row, M. N.; Rondan, N. G.; Wu, Y. D.; Brown, F. K.; Spellmeyer, D. C.; Metz, J. T.; Li, Y.; Loncharich, R. J. Science 1986, 231, 1108. (d) Masamune, S.; Kennedy, R. M.; Petersen, J. S.; Houk, K. N.; Wu, Y. D. J. Am. Chem. Soc. 1986, 108, 1986. (e) Eksterowez, J. E.; Houk, K. N. Chem. Rev. 1993, 93, 2439. (f) Wu, Y.-D.; Houk, K. N., Florez, J.; Trost. B M. J. Org. Chem. 1991, 56, 3656. (g) Wu, Y.-D.; Tucker, J. A.; Houk, K. N. J. Am. Chem. Soc. 1991, 113, 5018. (h) Broeker, J. L.; Hoffmann, R. W.; Houk, K. N. J. Am. Chem. Soc. 1991, 113, 5006.
25. 6f-h investigated stereoselectivities of the reductions of ketones and conformational analysis of chiral alkenes and oxonium ions using ab initio calculations; they developed an improved MM2 force field which qualitatively reproduces observed stereoselectivities: (a) Jones, D. K.; Liotta, D. C.; Shinkai, I.; Mathre, D. J. J. Org. Chem. 1993, 58, 799. (b) Houk. K. N.; Rondan, N. G.; Wu, Y. D.; Metz, J. T.; Paddon-Row, M. N. Tetrahedron 1984, 40, 2257. (c) Houk, K. N.; Paddon-Row, M. N.; Rondan, N. G.; Wu, Y. D.; Brown, F. K.; Spellmeyer, D. C.; Metz, J. T.; Li, Y.; Loncharich, R. J. Science 1986, 231, 1108. (d) Masamune, S.; Kennedy, R. M.; Petersen, J. S.; Houk, K. N.; Wu, Y. D. J. Am. Chem. Soc. 1986, 108, 1986. (e) Eksterowez, J. E.; Houk, K. N. Chem. Rev. 1993, 93, 2439. (f) Wu, Y.-D.; Houk, K. N., Florez, J.; Trost. B M. J. Org. Chem. 1991, 56, 3656. (g) Wu, Y.-D.; Tucker, J. A.; Houk, K. N. J. Am. Chem. Soc. 1991, 113, 5018. (h) Broeker, J. L.; Hoffmann, R. W.; Houk, K. N. J. Am. Chem. Soc. 1991, 113, 5006.
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28. Baker, J. J. Comput. Chem. 1986, 7, 385.
29. The two-dimensional energy maps generated by MNDO or by MM2 force field differ somewhat from the one generated by the AM1 method. However, the relative differences in energies of the calculated A and B conformera remain small.
30. Dewar, M. J. S.; Healy, E F.; Stewart, J. J. P. J. Chem. Soc., Faraday Trans. 2 1984, 3, 227.
31. McIver, J.; Komornicki, A. J. Am. Chem. Soc. 1972, 94, 2625.
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35. 2b
36. s conformer, the same complex that is formed more efficiently directly from B.
37. (a) Eliel, E. L. Stereochemistry of Carbon Compounds; McGraw-Hill: New York, 1962; p 149.
38. (b) For a more recent discussion, examples, and references, see: Eliel, E. L.; Wilen, S. H. Stereochemistry of Organic Compounds; John Wiley & Sons; New York, 1994; Chapters 10.2 and 14.4.
39. s were quite different, the relative energy differences within each method are similar.
40. (a) In Scheme 1, the two prostereogeneic B-R substituants in the B-Ipc-9-BBN molecule are smaller in size than the Ipc substituent. The subscripts s and r describe the respective configurations of the developing chiral carbon in the CD complex and in the transition state TS.
41. 3 structure appearing on the reaction path between the two reactants and the transition state that follows.
42. (a) Zefirov, N. S.; Palyulin, V. A. Zh. Org. Chem. 1979, 15, 1098.
43. (b) Zefirov, N. S. Tetrahedron 1977, 33, 2719.
44. (a) Curtin, D. Y. Rec. Chem. Prog. 1954, 15, 111.
45. (b) For extensive discussion of the conformation/reactivity relationships, the Curtin-Hammett principle, and kinetic analyses, see: Seeman, J. I. Chem. Rev. 1983, 83, 83.
46. (c) Winstein, S.; Holness, N. J. J. Am. Chem. Soc. 1955, 77, 5562.
47. (d) Eliel, E. L.; Ro, R. S. Chem. Ind. (London) 1956, 251.
48. Hutchins, R. O. J. Org. Chem. 1977, 42, 920.
49. For the discussion of additivity of conformational energies, see ref 16b, Chapter 11.4.
50. Reference 16b: (a) p 697; (b) p 696. (c) p 699. The enthalpy rather than the free energy of the i-Pr group is used here.
51. 1′-Hond in the CD complex resemble the relationship of the two primary C-H bonds in the "gauche" conformation of butane: ref 16b, p 600.
52. Mikhailov reported that the "reorganization energy" for the conversion of boron from trigonal to tetragonal configuration is 6-10 kcal/mol: Mikhailov, B. M.; Baryshnikova, T. K.; Shashov, A. S. J. Organomet. Chem. 1981, 219, 301.
53. The bond-making and bond-breaking contributions to the overall activation energy should be the same in both reaction pathways.