Ab initio computational examination of carbonyl reductions by borane: The importance of Lewis acid-base interactions

Journal of Organic Chemistry

Volumn 61, Issue 24, 1996, Pages 8378-8385

  DiMare, Marcello ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000356059     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo961159q     Document Type: Article

References (65)

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12. The ab initio method used here affords a diborane dissociation energy of 31.3 kcal/mol. See the following and references cited therein: (a) Page, M.; Adams, G.; Binkley, J. S.; Melius, C. F. J. Phys. Chem. 1987, 91, 2675-2678. (b) Bock, C. W.; Trachtman, M.; Murphy, C.; Muschert, B.; Mains, G. J. J. Phys. Chem. 1992, 95, 2339-2344.
13. The ab initio method used here affords a diborane dissociation energy of 31.3 kcal/mol. See the following and references cited therein: (a) Page, M.; Adams, G.; Binkley, J. S.; Melius, C. F. J. Phys. Chem. 1987, 91, 2675-2678. (b) Bock, C. W.; Trachtman, M.; Murphy, C.; Muschert, B.; Mains, G. J. J. Phys. Chem. 1992, 95, 2339-2344.
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19. For a review of Lewis acid-carbonyl interactions, see: Shambayati, S.; Schreiber, S. L. In Comprehensive Organic Synthesis: Additions to C-X π Bonds, Part 1; Schreiber, S. L., Ed.; Pergamon Press: Oxford, 1991; Vol. 1, pp 283-324.
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26. For the most recent computational work in the area and a summary of past work, see: (a) Wang, X.; Li, Y.; Wu, Y.-D.; Paddon-Row, M. N.; Rondan, N. G.; Houk, K. N. J. Org. Chem. 1990, 55, 2601-2609. (b) Hommes, N. J. R. V. E.; Schleyer, P. v. R. J. Org. Chem. 1991, 56, 4074-4076.
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35. Frisch, M. J.; Trucks, G. W.; Head-Gordon, M.; Gill, P. M. W.; Wong, M. W.; Foresman, J. B.; Johnson, B. G.; Schlegel, H. B.; Robb, M. A.; Replogle, E. S.; Gomperts, R.; Andres, J. L.; Raghavachari, K.; Binkley, J. S.; Gonzalez, C.; Martin, R. L.; Fox, D. J.; Defrees, D. J.; Baker, J.; Stewart, J. J. P.; Pople, J. A. Gaussian 92, Revision B; Gaussian, Inc.: Pittsburgh, PA, 1992.
36. 6-31G(d): Hariharan, P. C.; Pople, J. A. Theor. Chim. Acta 1973, 28, 213-222. Francl, M. M.; Pietro, W. J.; Hehre, W. J.; Binkley, J. S.; Gordon, M. S.; DeFrees, D. J.; Pople, J. A. J. Chem. Phys. 1982, 77, 3654-3665. 6-31+G(d,p): Spitznagel, G. W.; Clark, T.; Chandrasekhar, J.; Schleyer, P. v. R. J. Comput. Chem. 1982, 3, 363-371. Clark, T.; Chandrasekhar, J.; Spitznagel, G. W.; Schleyer, P. v. R. J. Comput. Chem. 1983, 4, 294-301.
37. 6-31G(d): Hariharan, P. C.; Pople, J. A. Theor. Chim. Acta 1973, 28, 213-222. Francl, M. M.; Pietro, W. J.; Hehre, W. J.; Binkley, J. S.; Gordon, M. S.; DeFrees, D. J.; Pople, J. A. J. Chem. Phys. 1982, 77, 3654-3665. 6-31+G(d,p): Spitznagel, G. W.; Clark, T.; Chandrasekhar, J.; Schleyer, P. v. R. J. Comput. Chem. 1982, 3, 363-371. Clark, T.; Chandrasekhar, J.; Spitznagel, G. W.; Schleyer, P. v. R. J. Comput. Chem. 1983, 4, 294-301.
38. 6-31G(d): Hariharan, P. C.; Pople, J. A. Theor. Chim. Acta 1973, 28, 213-222. Francl, M. M.; Pietro, W. J.; Hehre, W. J.; Binkley, J. S.; Gordon, M. S.; DeFrees, D. J.; Pople, J. A. J. Chem. Phys. 1982, 77, 3654-3665. 6-31+G(d,p): Spitznagel, G. W.; Clark, T.; Chandrasekhar, J.; Schleyer, P. v. R. J. Comput. Chem. 1982, 3, 363-371. Clark, T.; Chandrasekhar, J.; Spitznagel, G. W.; Schleyer, P. v. R. J. Comput. Chem. 1983, 4, 294-301.
39. 6-31G(d): Hariharan, P. C.; Pople, J. A. Theor. Chim. Acta 1973, 28, 213-222. Francl, M. M.; Pietro, W. J.; Hehre, W. J.; Binkley, J. S.; Gordon, M. S.; DeFrees, D. J.; Pople, J. A. J. Chem. Phys. 1982, 77, 3654-3665. 6-31+G(d,p): Spitznagel, G. W.; Clark, T.; Chandrasekhar, J.; Schleyer, P. v. R. J. Comput. Chem. 1982, 3, 363-371. Clark, T.; Chandrasekhar, J.; Spitznagel, G. W.; Schleyer, P. v. R. J. Comput. Chem. 1983, 4, 294-301.
40. Pople, J. A.; Scott, A. P.; Wong, M. W.; Radom, L. Isr. J. Chem. 1993, 33, 345-350. In several instances, ZPE corrections were obtained from MP2/6-31+G(d,p) calculations. These were scaled by 0.9646 (see preceding citation).
41. See the following and references cited therein: Dvorak, M. A.; Ford, R. S.; Suenram, R. D.; Lovas, F. J.; Leopold, K. R. J. Am. Chem. Soc. 1992, 114, 108-115.
42. This is supported by the increased C=O and decreased C-Cl bond distances on changing from HF to MP2 theory. With the 6-31G-(d) basis set, the C=O bond lengths are 1.1726 and 1.2240 Å using HF and MP2 theory, respectively. Similarly, the C-Cl bond lengths are 1.7681 and 1.734 Å for HF and MP2 theory, respectively.
43. During the course of this work, 3 was discovered to have been computationally characterized using slightly different methods; see: (a) McKee, M. L. J. Phys. Chem. 1992, 96, 5380-5385. (b) Sakai, S. Chem. Phys. Lett. 1994, 277, 288-292. A related adduct between hydrogen sulfide and diborane has been the subject of another paper, see: Mebel, A. M.; Musaev, D. G.; Morokuma, K. J. Phys. Chem. 1993, 97, 7543-7552.
44. During the course of this work, 3 was discovered to have been computationally characterized using slightly different methods; see: (a) McKee, M. L. J. Phys. Chem. 1992, 96, 5380-5385. (b) Sakai, S. Chem. Phys. Lett. 1994, 277, 288-292. A related adduct between hydrogen sulfide and diborane has been the subject of another paper, see: Mebel, A. M.; Musaev, D. G.; Morokuma, K. J. Phys. Chem. 1993, 97, 7543-7552.
45. During the course of this work, 3 was discovered to have been computationally characterized using slightly different methods; see: (a) McKee, M. L. J. Phys. Chem. 1992, 96, 5380-5385. (b) Sakai, S. Chem. Phys. Lett. 1994, 277, 288-292. A related adduct between hydrogen sulfide and diborane has been the subject of another paper, see: Mebel, A. M.; Musaev, D. G.; Morokuma, K. J. Phys. Chem. 1993, 97, 7543-7552.
46. In ref 5c, ester reduction aliquots (in THF) were hydrolyzed with (2,4-dinitrophenyl)hydrazine present in the hope of forming hydrazones of hydrolytically released aldehydes. It is difficult to assess the efficacy of this method.
47. Unpublished results of C. W. Lindsley and M. DiMare.
48. For entry into this literature, see: (a) Clark, T.; Wilhelm, D.; Schleyer, P. v. R. J. Chem. Soc., Chem. Commun. 1983, 606-608. (b) Brown, H. C.; Chandrasekharan, J. Gazz. Chim. Ital. 1987, 117, 517-523. (c) Tonachini, G. Gazz. Chim. Ital. 1988, 118, 149-151.
49. For entry into this literature, see: (a) Clark, T.; Wilhelm, D.; Schleyer, P. v. R. J. Chem. Soc., Chem. Commun. 1983, 606-608. (b) Brown, H. C.; Chandrasekharan, J. Gazz. Chim. Ital. 1987, 117, 517-523. (c) Tonachini, G. Gazz. Chim. Ital. 1988, 118, 149-151.
50. For entry into this literature, see: (a) Clark, T.; Wilhelm, D.; Schleyer, P. v. R. J. Chem. Soc., Chem. Commun. 1983, 606-608. (b) Brown, H. C.; Chandrasekharan, J. Gazz. Chim. Ital. 1987, 117, 517-523. (c) Tonachini, G. Gazz. Chim. Ital. 1988, 118, 149-151.
51. 3 and its constituents is 0.0 kcal/mol using calculated values of S° (principally due to the increased number of particles). The free energy of activation for this process is predicted to be slightly less than the enthalpic value reported. This is because the full entropic counterbalancing of enthalpic effects will not occur until very late in the reaction when ammonia and borane have dissociated (the majority of S° is derived from rotational and translational terms).
52. Whether a similar advantage exists with diborane adducts of Lewis bases is unclear. Attempts to locate an SN2-like transition state for transferring BHa from THF-B2H6 (6) to another Lewis base were unsuccessful.
53. No effort was made to locate a transition state leading to dimer 9.
54. A hydrogen-bridged dimer of methoxyborane could not be found. No effort was made to locate it as a transition state for degenerate hydrogen exchange.
55. The presence of THF or DMS would not be expected to modify the behavior of monoalkoxyboranes, because their coordination to a monoalkoxyborane would be weak relative to amines.
56. Also indicating later transition states, the transferring hydrogen to boron bond lengthens in the transition states for acetaldehyde reduction: borane, 1.218 Å; methoxyborane, 1.240 Å; dimethoxyborane, 1.270 Å.
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60. 3BH greatly accelerates the reaction of dialkoxyboranes with alcohols, see: Masuda, Y.; Nunokawa, Y.; Hoshi, M.; Arase, A. Chem. Lett. 1992, 349-352
61. (a) McAchran, G. E.; Shore, S. G. Inorg. Chem. 1966, 5, 2044-2046.
62. (b) Woods, W. G.; Strong, P. L. J. Am. Chem. Soc. 1966, 88, 4667-4671.
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64. Despite several attempts, an adduct of ammonia and dimethoxyborane could not be located at the HF/6-31G(d) level.
65. Dialkoxyboranes would have to be mild catalysts not to generate a marked autocatalytic effect or be detected by earlier vapor-phase kinetics (see ref 6).