Theory of 1,3-dipolar cycloadditions: Distortion/interaction and frontier molecular orbital models

Journal of the American Chemical Society

Volumn 130, Issue 31, 2008, Pages 10187-10198

  Ess, Daniel H ^a   Houk, K N ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ACETYLENE; CYCLOADDITION; ETHYLENE; LIGHTING; MOLECULAR ORBITALS; NITROGEN COMPOUNDS; QUANTUM CHEMISTRY;

ACTIVATION BARRIERS; AZOMETHINE; BARRIER HEIGHTS; CBS-QB3; CYCLOADDITIONS; DIPOLAR CYCLOADDITIONS; HIGH-ACCURACY; MEAN ABSOLUTE DEVIATION; MOLECULAR ORBITAL; MONOTONIC DECREASE; QUANTUM CHEMICAL CALCULATIONS; REACTION ENERGIES; REACTION THERMODYNAMICS;

ACTIVATION ENERGY;

ACETYLENE; ALKENE DERIVATIVE; ALKYNE; AMPHOLYTE; BETAINE DERIVATIVE; DIAZONIUM COMPOUND; ETHYLENE; IMINE; NITRILE; OXIDE;

ACCURACY; ARTICLE; ATOM; CYCLOADDITION; DIPOLE; ENERGY; GEOMETRY; MOLECULAR DYNAMICS; MOLECULAR INTERACTION; MOLECULAR MODEL; QUANTITATIVE ANALYSIS; QUANTUM CHEMISTRY; REACTION ANALYSIS; SUBSTITUTION REACTION; THEORETICAL STUDY; THERMODYNAMICS;

HETEROCYCLIC COMPOUNDS; MODELS, CHEMICAL; MODELS, MOLECULAR; QUANTUM THEORY; THERMODYNAMICS;

EID: 48749096518     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja800009z     Document Type: Article

References (119)

1. Synthetic Applications of 1,3-Dipolar Cycloaddition Chemistry Toward Heterocycles and Natural Products; Padwa, A.; Pearson, W. H., Eds.; Wiley: New York, 2002.
2. (a) Collman, J. P.; Devaraj, N. K.; Chidsey, C. E. D. Langmuir 2004, 20, 1051.
3. (b) Speers, A. E.; Adam, G. C.; Cravatt, B. F. J. Am. Chem. Soc. 2003, 125, 4686.
4. Krasinski, A.; Radic, Z.; Manetsch, R.; Raushel, J.; Taylor, P.; Sharpless, K. B.; Kolb, H. C. J. Am. Chem. Soc. 2005, 127, 6686.
5. Seo, T. S.; Bai, X.; Ruparel, H.; Li, Z.; Turro, N. J.; Ju, J. Proc. Natl. Acad. Sci. USA 2004, 101, 5488.
6. KoIb, H. C.; Finn, M. G.; Sharpless, K. B. Angew. Chem., Int. Ed. 2001, 40, 2004.
7. (a) Huisgen, R. Angew. Chem. Chem., Int. Ed. Engl. 1963, 2, 565.
8. (b) Huisgen, R. Angew. Chem. Chem., Int. Ed. Engl. 1963, 2, 633.
9. (c) Huisgen, R. Angew. Chem. Chem., Int. Ed. Engl. 1968, 7, 321.
10. (d) Huisgen, R. In 1,3-Dipolar Cycloaddition Chemistry; Padwa, A., Ed.; John Wiley and Sons: New York, 1984; Vol. 1.
11. Woodward, R. B.; Hoffmann, R. Angew. Chem., Int. Ed. Engl. 1969, 8, 781.
12. (a) Sustmann, R. Tetrahedron Lett. 1971, 12, 2717.
13. (b) Sustmann, R.; Trill, H. Angew. Chem. Chem., Int. Ed. Engl. 1972, 11, 838.
14. (c) Houk, K. N. In 1,3-Dipolar Cycloaddition Chemistry; Padwa, A., Ed.; John Wiley and Sons: New York, 1984; Vol. 2.
15. (a) Houk, K. N.; Sims, J.; Duke, R. E., Jr.; Strozier, R. W.; George, J. K. J. Am. Chem. Soc. 1973, 95, 7287.
16. (b) Houk, K. N.; Sims, J.; Watts, C. R.; Luskus, L. J. J. Am. Chem. Soc. 1973, 95, 7301.
17. (c) Bastide, J.; Ghandour, W. E.; Henri-Rousseau, O. Tetrahedron Lett. 1972, 41, 4225.
18. (a) Salem, L. J. Am. Chem. Soc. 1968, 90, 543.
19. (b) Salem, L. J. Am. Chem. Soc. 1968, 90, 553.
20. (a) Fukui, K. Acc. Chem. Res. 1971, 4, 57.
21. (b) Houk, K. N. Acc. Chem. Res. 1975, 8, 361.
22. (c) Houk, K. N. In Pericyclic Reactions; Marchand. A. P.; Lehr, R. E., Eds.; Academic Press: New York, 1977; Vol. 2, p 181.
23. (d) Fukui, K. Angew. Chem., Int. Ed. Engl. 1982, 21, 801.
24. For recent uses of FMO theory for 1,3-dipolar cycloadditions, see: (a) Jikyo, T.; Schatz, J.; Maas, G. J. Phys. Org. Chem. 2003, 16, 504.
25. (b) Marakchi, K.; Kabbaj, O.; Komiha, N.; Jalal, N.; Esseffar, M. J. Mol. Struct. (THEOCHEM) 2003, 620, 271.
26. (c) Domingo, L. R.; Benchouk, W.; Mekelleche, S. M. Tetrahedron 2007, 63, 4464.
27. (d) Li, X-B.; Song, Q-H. Heteroat. Chem 2007, 3, 203.
28. (a) Ess, D. H.; Jones, G. O.; Houk, K. H. Adv. Synth. Catal. 2006, 348, 2337.
29. (b) Pross, A.; Shaik, S. S. Acc. Chem. Res. 1983, 16, 363-370.
30. (a) Murdoch, J. R. J. Am. Chem. Soc. 1983, 105, 2660.
31. (b) Murdoch, J. R. J. Am. Chem. Soc. 1983, 105, 2667.
32. (c) Murdoch, J. R.; Morgan, Y. C. J. Am. Chem. Soc. 1984, 106, 4735.
33. (d) Miller, A. R. J. Am. Chem. Soc. 1978, 100, 1984.
34. Evans, M. G.; Polanyi, M. Trans. Faraday Soc. 1938, 34, 614.
35. Koeppl, G. W.; Kresge, A. J. J. Chem. Soc., Chem. Commun. 1973, 371.
36. Marcus, R. A. Pure Appl. Chem. 1997, 69, 13.
37. Ess, D. H.; Houk, K. N. J. Am. Chem. Soc. 2007, 129, 10646.
38. (a) Walch, S. P.; Goddard, W. A., III. J. Am. Chem. Soc. 1975, 97, 5319.
39. (b) Kahn, S. D.; Hehre, W. J.; Pople, J. A. J. Am. Chem. Soc. 1987, 109, 1871.
40. (c) Hiberty, P. C.; Leforestier, C. J. Am. Chem. Soc. 1978, 100, 2012.
41. (a) Huisgen, R. J. Org. Chem. 1968, 33, 2291.
42. (b) Firestone, R. A. J. Org. Chem. 1968, 33, 2285.
43. (a) Houk, K. N.; Firestone, R. A.; Munchausen, L. L.; Mueller, P. H.; Arison, B. H.; Garcia, L. A. J. Am. Chem. Soc. 1985, 107, 7227.
44. (b) Houk, K. N.; González, J.; Li, Y. Acc. Chem. Res. 1995, 28, 81.
45. (a) McDouall, J. J. W.; Robb, M. A.; Niazi, U.; Bernardi, F.; Schlegel, H. B. J. Am. Chem. Soc. 1987, 109, 4642.
46. (b) Previous CI calculations actually favored a diradical mechanism: Hiberty, P. C.; Ohanessian, G.; Schlegel, H. B. J. Am. Chem. Soc. 1983, 105, 719.
47. Nguyen, J. T.; Chandra, A. K.; Sakai, S.; Morokuma, K. J. Org. Chem. 1999, 64.
48. Su, M-D.; Liao, H-Y.; Chung, W-S.; Chu, S-Y. J. Org. Chem. 1999, 64, 6710.
49. Marcus, R. A. J. Chem. Phys. 1956, 24, 966.
50. Dimroth, O. Angew. Chem. 1933, 46, 571.
51. Frisch, M. J.; et al. Gaussian 03, Revision C.02; Gaussian, Inc: Wallingford CT, 2004.
52. Yamaguchi, K.; Takahara, Y.; Fueno, T.; Houk, K. N. Theor. Chim. Acta 1988, 73, 337.
53. (a) Montgomery, J. A.; Frisch, M. J.; Ochterski, J. W.; Petersson, G. A. J. Chem. Phys. 2000, 112, 6532.
54. (b) Montgomery, J. A.; Frisch, M. J.; Ochterski, J. W.; Petersson, G. A. J. Chem. Phys. 1999, 110, 2822.
55. (c) Petersson, G. A.; Malick, D. K.; Wilson, W. G.; Ochterski, J. W.; Montgomery, J. A.; Frisch, M. J. J. Chem. Phys. 1998, 109, 10570.
56. (a) Politzer, P.; Abu-Awwad, F. Theor. Chem. Acc. 1998, 99, 83.
57. (b) Kar, T.; Ángyán, J. G.; Sannigrahi, A. B. J. Phys. Chem. A 2000, 104, 9953.
58. (c) Zhang, G.; Musgrave, C. B. J. Phys. Chem. A 2007, 111, 1554.
59. Ess, D. H.; Houk, K. N. J. Phys. Chem. A 2005, 109, 9542.
60. Values taken from the National Institute of Standards and Technology (NIST) Chemistry Webbook (NIST Standard Reference Database Number 69, June 2005 Release).
61. The only parent reaction studied experimentally is that of diazomethane cycloaddition to ethylene in DMF. See: (a) Geittner, J.; Huisgen, R.; Sustmann, R. Tetrahedron Lett. 1977, 10, 881.
62. (b) Geittner, J.; Huisgen, R.; Reissig, H.-U. Heterocycles 1978, 11, 109.
63. ST value for the reactants gives a lower barrier, earlier transition state, and greater exothermic reaction energy, See refs 23, 24, and the following: (a) Liao, H-Y.; Su, M-D.; Chung, W-S.; Chu, S-Y. Int. J. Quant. Chem. 2001, 83, 318.
64. (b) Sakai, S.; Nguyen, M. T. J. Phys. Chem. A 2004, 108, 9169.
65. (c) Sakai, S.; Nguyen, M. T. J. Phys. Chem. A 2000, 104, 922.
66. (a) Nguyen, M. T.; Matus, M. H.; Lester, W. A., Jr.; Dixon, D. A. J. Phys. Chem. A 2008, 112, 2082.
67. (b) Le, H. T.; Flock, M.; Nguyen, M. T. J. Chem. Phys. 2000, 112, 7008.
68. (c) Van Veen, E. H. Chem. Phys. Lett. 1976, 41, 540.
69. (a) Hammond, G. S. J. Am. Chem. Soc. 1955, 77, 334.
70. (b) Evans, M. G.; Polanyi, M. Trans. Faraday Soc. 1938, 34, 11.
71. Poppinger, D. J. Am. Chem. Soc. 1975, 97, 7486.
72. For dipoles 1-6, only the stepwise transition state for HCNO + acetylene was located with UB3LYP.
73. 2 values.
74. (a) Valentin, C. D.; Freccero, M.; Gandolfi, R.; Rastelli, A. J. Org. Chem. 2000, 65, 6112.
75. (a) Strozier, R. W.; Caramella, P.; Houk, K. N. J. Am. Chem. Soc. 1979, 101, 1340.
76. (b) Houk, K. N.; Rondan, N. G.; Schleyer, P.v-R.; Kaufmann, E.; Clark, T. J. Am. Chem. Soc. 1985, 107, 2821.
77. (c) Rondan, N. G.; Domelsmith, L. N.; Houk, K. N.; Bowne, A. T.; Levin, R. H. Tetrahedron Lett. 1979, 35, 3237.
78. (a) Huisgen, R.; Mloston, G.; Langhals, E. J. Am. Chem. Soc. 1986, 108, 6401.
79. (b) Huisgen, R.; Mioston, G.; Langhals, E. J. Org. Chem. 1986, 51, 4085.
80. (c) Weber, A.; Sauer, J. Tetrahedron Lett. 1998, 39, 807.
81. (d) Vivanco, S.; Lecea, B.; Arrieta, A.; Prieto, P.; Morao, I.; Linden, A.; Cossio, F. P. J. Am. Chem. Soc. 2000, 122, 6078.
82. (a) Kitaura, K.; Morokuma, K. Int. J. Quant. Chem. 1976, 10, 325.
83. (b) Nagase, S.; Morokuma, K. J. Am. Chem. Soc. 1978, 100, 1666.
84. (c) Houk, K. N.; Gandour, R. W.; Strozier, R. W.; Rondan, N. G.; Paquette, L. A. J. Am. Chem. Soc. 1979, 101, 6797.
85. (d) Froese, R. D. J.; Coxon, J. M.; West, S. C.; Morokuma, K. J. Org. Chem. 1997, 62, 6991.
86. (e) Koga, N.; Ozawa, T.; Morokuma, K. J. Phys. Org. Chem. 1990, 3, 519.
87. (f) Coxen, J. M.; Grice, S. T.; Maclagan, R. G. A. R.; McDonald, D. Q. J. Org. Chem. 1990, 55, 3804.
88. (g) Coxon, J. M.; Rroese, R. D. J.; Ganguly, B.; Marchand, A. P.; Morokuma, K. J. Synnlett 1999, 11, 1681.
89. (h) Avalos, M.; Babiano, R.; Bravo, J. L.; Cintas, P.; Jiménez, J.; Palacios, J.; Silva, M. A. J. Org. Chem. 2000, 65, 6613.
90. (i) Geetha, K.; Dinadayalane, T. C.; Sastry, G. N. J. Phys. Org. Chem. 2003, 16, 298.
91. (j) Manoharan, M.; Venuvanalingam, P. J. Chem. Soc., Perkin Trans. 2 1997, 1799.
92. (k) Kavitha, K.; Manoharan, M.; Venuvanalingam, P. J. Org. Chem. 2005, 70, 2528.
93. (l) Kavitha, K.; Venuvanalingam, P. Int. J. Quant. Chem. 2005, 104, 67.
94. (m) Blowers, P.; Ford, L.; Masel, R. J. Phys. Chem. A 1998, 102, 9267.
95. (a) Bickelhaupt, F. M. J. Comput. Chem. 1999, 20, 114.
96. (b) Velde, G. T.; Bickelhaupt, F. M.; Baerends, E. J.; Guerra, C. F.; Gisbergen, S. J. A. V.; Snijders, J. G.; Ziegler, T. J. Comput. Chem. 2001, 22, 931.
97. (c) Diefenbach, A.; Bickelhaupt, F. M. J. Chem. Phys. 2001, 115, 4030.
98. (d) Diefenbach, A.; Bickelhaupt, F. M. J. Phys. Chem. A 2004, 108, 8460.
99. (e) Diefenbach, A.; Bickelhaupt, F. M. J. Organomet. Chem. 2005, 690, 2191.
100. (f) Diefenbach, A.; de Jong, G. T.; Bickelhaupt, F. M. Mol. Phys. 2005, 103, 995.
101. (g) Diefenbach, A.; de Jong, G. T.; Bickelhaupt, F. M. J. Chem. Theory Comput. 2005, 1, 286.
102. (h) Stralen, J. N. P.v.; Bickelhaupt, F. M. Organometallics 2006, 25, 4260.
103. (i) de Jong, G. T.; Visser, R.; Bickelhaupt, F. M. J. Organomet. Chem. 2006, 691, 4341.
104. (j) de Jong, G. T.; Bickelhaupt, F. M. Chem. Phys. Chem. 2007, 8, 1170.
105. (k) de Jong, G. T.; Bickelhaupt, F. M. J. Chem. Theory Comput. 2007, 3, 514.
106. Ziegler and Rauk have considered distortion energy as apart of their extended transition state method: (a) Ziegler, T.; Rauk, A. Theor. Chim. Acta 1977, 46, 1.
107. (b) Ziegler, T.; Rauk, A. lnorg. Chem. 1979, 18, 1755.
108. (c) Bickelhaupt, F. M.; Ziegler, T.; Schleyer, P. v. R. Organometallics 1995, 14, 2288.
109. d‡.
110. Jones, G. O.; Ess, D. H.; Houk, K. N. Helv. Chim. Acta 2005, 88, 1702.
111. d‡, with the intercept equal to zero. Ess, D. H.; Khaliullin, R. Z.; Head-Gordon, M.; Houk, K. N. Manuscript in preparation.
112. For a definitive study on the activation barriers for the dipolar cycloadditions of ozone with ethylene and acetylene, see: Wheeler, S. E.; Ess, D. H.; Houk, K. N. J. Phys. Chem. A 2008, 112, 1798.
113. r. Yates has proposed an alternative form of the Marcus equation that includes an eccentricity or asymmetry variable (ranging from 0 to 1) in front of the intrinsic barrier term. See: Yates, K. J. Am. Chem. Soc. 1986, 108, 6511. Point 2 was suggested by personal communication with R. Marcus.
114. (b) When reactant and product parabola curvature are nearly equal, there is typically much better correlation between activation barriers and reaction energies. See for example: Alabugin, I. V.; Manoharan, M.; Breiner, B.; Lewis, F. D. J. Am. Chem. Soc. 2003, 125, 9329.
115. Caramella, P.; Houk, K. N. J. Am. Chem. Soc. 1976, 98, 6397.
116. Here we are concerned with dipolarophile reactivity, not regioselectivity differences. Rastelli and co-workers have previously shown that dipolarophile distortion energy is important for diasterofacial selectivity in 1,3-dipolar cycloadditions with cyclobutenes. See for example: (a) Bagatti, M.; Rastelli, A.; Burdisso, M.; Gandolfi, R. J. Phys. Org. Chem. 1992, 5, 819.
117. (b) Bagatti, M.; Ori, A.; Rastelli, A.; Burdisso, M.; Gandolfi, R. J. Chem. Soc. Perkin Trans. 2 1992, 1657.
118. (c) Rastelli, A.; Bagatti, M.; Ori, A.; Gandolfi, R.; Burdisso, M. J. Chem. Soc. Faraday Trans. 1993, 89, 29.
119. (d) Rastelli, A.; Bagatti, M.; Gandolfi, R. J. Chem. Soc. Faraday Trans. 1993, 89, 3913.