Clarification of the mechanism of the cascade reactions between amino-substituted heterocycles and 1,3,5-triazines

Journal of Organic Chemistry

Volumn 70, Issue 3, 2005, Pages 998-1005

  Yu, Zhi Xiang ^a,c   Dang, Qun ^b   Wu, Yun Dong ^a,c  

^a HONG KONG UNIVERSITY OF SCIENCE AND TECHNOLOGY   (Hong Kong)

^b Metabasis Therapeutics Inc   (United States)

^c PEKING UNIVERSITY   (China)

Author keywords

[No Author keywords available]

Indexed keywords

AMMONIA; REACTION KINETICS; SUBSTITUTION REACTIONS;

1,3,5-TRIAZINES; GAS PHASE; IMIDAZOLES; INVERSE-ELECTRON DEMAND DIELS-ALDER (IDA) REACTIONS;

AMINES;

AMMONIA; HETEROCYCLIC COMPOUND; IMIDAZOLE; PYRAZOLE; PYRROLE; TRIAZINE;

AMINO ACID SUBSTITUTION; ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; CYCLOADDITION; DIELS ALDER REACTION; ELECTRON; MATHEMATICAL COMPUTING;

EID: 13244277643     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo049248n     Document Type: Article

References (93)

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8. For recent reviews on Diels-Alder reactions, see: (a) Carruthers, W. Cycloaddition Reactions in Organic Synthesis; Pergamon: Oxford, 1990. (b) Fringuelli, F.; Taticchi, A. Dienes in the Diels-Alder Reaction; John Willey & Sons, Inc.: New York, 1990. (c) Boger, D. L.; Weinreb, S. N. Hetero Diels-Alder Methodology in Organic Synthesis. In Organic Chemistry, A Series of Monographs; Academic Press: New York, 1987; No. 47. (d) Oppolzer, W. In Comprehensive Organic Synthesis; Paquette, L. A., Ed.; Pergamon: Oxford, 1991; Vol. 5, p 315. (e) Roush, W. R. In Comprehensive Organic Synthesis; Paquette, L. A., Ed.; Pergamon: Oxford, 1991; Vol. 5, p 513. (f) Coxon, J. M.; McDonald, D. Q.; Steel, P. J. In Advances in Detailed Reaction Mechanisms; Coxon, J. M., Ed.; JAI Press: Greenwich, 1994. (g) Houk, K. N.; Li, Yi.; Evanseck, J. D. Angew. Chem., Int. Ed. Engl. 1992, 31, 682. (h) Sustmann, R. Tetrahedron Lett. 1971, 2721. (i) Sauer J.; Sustmann, R. Angew. Chem., Int. Ed. Engl. 1980, 19, 779. (j) Corey, E. J. Angew. Chem., Int. Ed. 2002, 41, 1650. (k) Nicolaou, K. C.; Snyder, S. A.; Montagnon, T.; Vassilikogiannakis, G. Angew. Chem., Int. Ed. 2002, 41, 1668.
9. For recent reviews on Diels-Alder reactions, see: (a) Carruthers, W. Cycloaddition Reactions in Organic Synthesis; Pergamon: Oxford, 1990. (b) Fringuelli, F.; Taticchi, A. Dienes in the Diels-Alder Reaction; John Willey & Sons, Inc.: New York, 1990. (c) Boger, D. L.; Weinreb, S. N. Hetero Diels-Alder Methodology in Organic Synthesis. In Organic Chemistry, A Series of Monographs; Academic Press: New York, 1987; No. 47. (d) Oppolzer, W. In Comprehensive Organic Synthesis; Paquette, L. A., Ed.; Pergamon: Oxford, 1991; Vol. 5, p 315. (e) Roush, W. R. In Comprehensive Organic Synthesis; Paquette, L. A., Ed.; Pergamon: Oxford, 1991; Vol. 5, p 513. (f) Coxon, J. M.; McDonald, D. Q.; Steel, P. J. In Advances in Detailed Reaction Mechanisms; Coxon, J. M., Ed.; JAI Press: Greenwich, 1994. (g) Houk, K. N.; Li, Yi.; Evanseck, J. D. Angew. Chem., Int. Ed. Engl. 1992, 31, 682. (h) Sustmann, R. Tetrahedron Lett. 1971, 2721. (i) Sauer J.; Sustmann, R. Angew. Chem., Int. Ed. Engl. 1980, 19, 779. (j) Corey, E. J. Angew. Chem., Int. Ed. 2002, 41, 1650. (k) Nicolaou, K. C.; Snyder, S. A.; Montagnon, T.; Vassilikogiannakis, G. Angew. Chem., Int. Ed. 2002, 41, 1668.
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16. For recent investigations of IDA reactions, see: (a) Liu, J.; Niwayama, S.; You, Y.; Houk, K. N. J. Org. Chem. 1998, 63, 1064. (b) Thorhauge, J.; Johannsen, M.; Jorgensen, K. A. Angew. Chem., Int. Ed. 1998 37, 2404. (c) Evans, A. D.; Olhava, E. J.; Johnson, J. S.; Janey, J. M. Angew. Chem., Int. Ed. 1998, 37, 3372. (d) Wijnen, J. W.; Zavarise, S.; Engberts, B. F. N.; Charton, M. J. Org. Chem. 1996, 61, 2001. (e) Boger, D. L.; Corbett, W. L.; Curran, T. T.; Kasper, A. M. J. Am. Chem. Soc. 1991, 113, 1713. (f) Markó, I. E.; Evans, G. R. Tetrahedron Lett. 1994, 35, 2767. (g) Zhou, J.-C.; Wyler, H. Helv. Chim. Acta 1999, 82, 1122.
17. For recent investigations of IDA reactions, see: (a) Liu, J.; Niwayama, S.; You, Y.; Houk, K. N. J. Org. Chem. 1998, 63, 1064. (b) Thorhauge, J.; Johannsen, M.; Jorgensen, K. A. Angew. Chem., Int. Ed. 1998 37, 2404. (c) Evans, A. D.; Olhava, E. J.; Johnson, J. S.; Janey, J. M. Angew. Chem., Int. Ed. 1998, 37, 3372. (d) Wijnen, J. W.; Zavarise, S.; Engberts, B. F. N.; Charton, M. J. Org. Chem. 1996, 61, 2001. (e) Boger, D. L.; Corbett, W. L.; Curran, T. T.; Kasper, A. M. J. Am. Chem. Soc. 1991, 113, 1713. (f) Markó, I. E.; Evans, G. R. Tetrahedron Lett. 1994, 35, 2767. (g) Zhou, J.-C.; Wyler, H. Helv. Chim. Acta 1999, 82, 1122.
18. For recent investigations of IDA reactions, see: (a) Liu, J.; Niwayama, S.; You, Y.; Houk, K. N. J. Org. Chem. 1998, 63, 1064. (b) Thorhauge, J.; Johannsen, M.; Jorgensen, K. A. Angew. Chem., Int. Ed. 1998 37, 2404. (c) Evans, A. D.; Olhava, E. J.; Johnson, J. S.; Janey, J. M. Angew. Chem., Int. Ed. 1998, 37, 3372. (d) Wijnen, J. W.; Zavarise, S.; Engberts, B. F. N.; Charton, M. J. Org. Chem. 1996, 61, 2001. (e) Boger, D. L.; Corbett, W. L.; Curran, T. T.; Kasper, A. M. J. Am. Chem. Soc. 1991, 113, 1713. (f) Markó, I. E.; Evans, G. R. Tetrahedron Lett. 1994, 35, 2767. (g) Zhou, J.-C.; Wyler, H. Helv. Chim. Acta 1999, 82, 1122.
19. For IDA reactions in natural product synthesis, see: (a) Boger, D. L.; Honda, T.; Menezes, R. F.; Colletti, S. L. J. Am. Chem. Soc. 1994, 116, 5631. (b) Boger, D. L.; Honda, T.; Dang, Q. J. Am. Chem. Soc. 1994, 116, 5619. (c) Boger, D. L.; Colletti, S. L.; Honda, T.; Menezes, R. F. J. Am. Chem. Soc. 1994, 116, 5607. (d) Boger, D. L.; Menezes, R. F.; Honda, T. Angew. Chem., Int. Ed. Engl. 1993, 32, 273. (e) Boger, D. L.; Menezes, R. F.; Dang, Q. J. Org. Chem. 1992, 57, 4333. (f) Boger, D. L.; Menezes, R. F.; Dang, Q.; Yang, W. BioMed. Chem. Lett. 1992, 2, 261. (g) For related studies, see: Boger, D. L.; Kochanny, M. J. Org. Chem. 1994, 59, 4950. (h) Desimoni, G.; Tacconi, G.; Barco, A.; Pollini, G. P. Natural Product Synthesis through Pericyclic Reactions; ACS Monograph 180; American Chemical Society: Washington, DC, 1983. (i) Davies, D. E.; Gilchrist, T. L.; Roberts, T. G. J. Chem. Soc., Perkin Trans. 1 1983, 1275. (j) Schmidt R. R.; Maier, M. Tetrahedron Lett. 1982, 23, 1789. (k) Desimoni, G.; Tacconi, G. Chem. Rev. 1975, 75, 651 (l) Bodwell, G. J.; Li, J. Org. Lett. 2002, 4, 127. (m) Bodwell, G. J.; Li, J. Angew. Chem., Int. Ed. 2002, 41, 3261. (n) Benson, S. C.; Lee, L.; Snyder, J. K. Tetrahedron Lett. 1996, 37, 5061. (o) Benson, S. C.; Lee, L.; Yang, L.; Snyder, J. K. Tetrahedron 2000, 65, 1165.
20. For IDA reactions in natural product synthesis, see: (a) Boger, D. L.; Honda, T.; Menezes, R. F.; Colletti, S. L. J. Am. Chem. Soc. 1994, 116, 5631. (b) Boger, D. L.; Honda, T.; Dang, Q. J. Am. Chem. Soc. 1994, 116, 5619. (c) Boger, D. L.; Colletti, S. L.; Honda, T.; Menezes, R. F. J. Am. Chem. Soc. 1994, 116, 5607. (d) Boger, D. L.; Menezes, R. F.; Honda, T. Angew. Chem., Int. Ed. Engl. 1993, 32, 273. (e) Boger, D. L.; Menezes, R. F.; Dang, Q. J. Org. Chem. 1992, 57, 4333. (f) Boger, D. L.; Menezes, R. F.; Dang, Q.; Yang, W. BioMed. Chem. Lett. 1992, 2, 261. (g) For related studies, see: Boger, D. L.; Kochanny, M. J. Org. Chem. 1994, 59, 4950. (h) Desimoni, G.; Tacconi, G.; Barco, A.; Pollini, G. P. Natural Product Synthesis through Pericyclic Reactions; ACS Monograph 180; American Chemical Society: Washington, DC, 1983. (i) Davies, D. E.; Gilchrist, T. L.; Roberts, T. G. J. Chem. Soc., Perkin Trans. 1 1983, 1275. (j) Schmidt R. R.; Maier, M. Tetrahedron Lett. 1982, 23, 1789. (k) Desimoni, G.; Tacconi, G. Chem. Rev. 1975, 75, 651 (l) Bodwell, G. J.; Li, J. Org. Lett. 2002, 4, 127. (m) Bodwell, G. J.; Li, J. Angew. Chem., Int. Ed. 2002, 41, 3261. (n) Benson, S. C.; Lee, L.; Snyder, J. K. Tetrahedron Lett. 1996, 37, 5061. (o) Benson, S. C.; Lee, L.; Yang, L.; Snyder, J. K. Tetrahedron 2000, 65, 1165.
21. For IDA reactions in natural product synthesis, see: (a) Boger, D. L.; Honda, T.; Menezes, R. F.; Colletti, S. L. J. Am. Chem. Soc. 1994, 116, 5631. (b) Boger, D. L.; Honda, T.; Dang, Q. J. Am. Chem. Soc. 1994, 116, 5619. (c) Boger, D. L.; Colletti, S. L.; Honda, T.; Menezes, R. F. J. Am. Chem. Soc. 1994, 116, 5607. (d) Boger, D. L.; Menezes, R. F.; Honda, T. Angew. Chem., Int. Ed. Engl. 1993, 32, 273. (e) Boger, D. L.; Menezes, R. F.; Dang, Q. J. Org. Chem. 1992, 57, 4333. (f) Boger, D. L.; Menezes, R. F.; Dang, Q.; Yang, W. BioMed. Chem. Lett. 1992, 2, 261. (g) For related studies, see: Boger, D. L.; Kochanny, M. J. Org. Chem. 1994, 59, 4950. (h) Desimoni, G.; Tacconi, G.; Barco, A.; Pollini, G. P. Natural Product Synthesis through Pericyclic Reactions; ACS Monograph 180; American Chemical Society: Washington, DC, 1983. (i) Davies, D. E.; Gilchrist, T. L.; Roberts, T. G. J. Chem. Soc., Perkin Trans. 1 1983, 1275. (j) Schmidt R. R.; Maier, M. Tetrahedron Lett. 1982, 23, 1789. (k) Desimoni, G.; Tacconi, G. Chem. Rev. 1975, 75, 651 (l) Bodwell, G. J.; Li, J. Org. Lett. 2002, 4, 127. (m) Bodwell, G. J.; Li, J. Angew. Chem., Int. Ed. 2002, 41, 3261. (n) Benson, S. C.; Lee, L.; Snyder, J. K. Tetrahedron Lett. 1996, 37, 5061. (o) Benson, S. C.; Lee, L.; Yang, L.; Snyder, J. K. Tetrahedron 2000, 65, 1165.
22. For IDA reactions in natural product synthesis, see: (a) Boger, D. L.; Honda, T.; Menezes, R. F.; Colletti, S. L. J. Am. Chem. Soc. 1994, 116, 5631. (b) Boger, D. L.; Honda, T.; Dang, Q. J. Am. Chem. Soc. 1994, 116, 5619. (c) Boger, D. L.; Colletti, S. L.; Honda, T.; Menezes, R. F. J. Am. Chem. Soc. 1994, 116, 5607. (d) Boger, D. L.; Menezes, R. F.; Honda, T. Angew. Chem., Int. Ed. Engl. 1993, 32, 273. (e) Boger, D. L.; Menezes, R. F.; Dang, Q. J. Org. Chem. 1992, 57, 4333. (f) Boger, D. L.; Menezes, R. F.; Dang, Q.; Yang, W. BioMed. Chem. Lett. 1992, 2, 261. (g) For related studies, see: Boger, D. L.; Kochanny, M. J. Org. Chem. 1994, 59, 4950. (h) Desimoni, G.; Tacconi, G.; Barco, A.; Pollini, G. P. Natural Product Synthesis through Pericyclic Reactions; ACS Monograph 180; American Chemical Society: Washington, DC, 1983. (i) Davies, D. E.; Gilchrist, T. L.; Roberts, T. G. J. Chem. Soc., Perkin Trans. 1 1983, 1275. (j) Schmidt R. R.; Maier, M. Tetrahedron Lett. 1982, 23, 1789. (k) Desimoni, G.; Tacconi, G. Chem. Rev. 1975, 75, 651 (l) Bodwell, G. J.; Li, J. Org. Lett. 2002, 4, 127. (m) Bodwell, G. J.; Li, J. Angew. Chem., Int. Ed. 2002, 41, 3261. (n) Benson, S. C.; Lee, L.; Snyder, J. K. Tetrahedron Lett. 1996, 37, 5061. (o) Benson, S. C.; Lee, L.; Yang, L.; Snyder, J. K. Tetrahedron 2000, 65, 1165.
23. For IDA reactions in natural product synthesis, see: (a) Boger, D. L.; Honda, T.; Menezes, R. F.; Colletti, S. L. J. Am. Chem. Soc. 1994, 116, 5631. (b) Boger, D. L.; Honda, T.; Dang, Q. J. Am. Chem. Soc. 1994, 116, 5619. (c) Boger, D. L.; Colletti, S. L.; Honda, T.; Menezes, R. F. J. Am. Chem. Soc. 1994, 116, 5607. (d) Boger, D. L.; Menezes, R. F.; Honda, T. Angew. Chem., Int. Ed. Engl. 1993, 32, 273. (e) Boger, D. L.; Menezes, R. F.; Dang, Q. J. Org. Chem. 1992, 57, 4333. (f) Boger, D. L.; Menezes, R. F.; Dang, Q.; Yang, W. BioMed. Chem. Lett. 1992, 2, 261. (g) For related studies, see: Boger, D. L.; Kochanny, M. J. Org. Chem. 1994, 59, 4950. (h) Desimoni, G.; Tacconi, G.; Barco, A.; Pollini, G. P. Natural Product Synthesis through Pericyclic Reactions; ACS Monograph 180; American Chemical Society: Washington, DC, 1983. (i) Davies, D. E.; Gilchrist, T. L.; Roberts, T. G. J. Chem. Soc., Perkin Trans. 1 1983, 1275. (j) Schmidt R. R.; Maier, M. Tetrahedron Lett. 1982, 23, 1789. (k) Desimoni, G.; Tacconi, G. Chem. Rev. 1975, 75, 651 (l) Bodwell, G. J.; Li, J. Org. Lett. 2002, 4, 127. (m) Bodwell, G. J.; Li, J. Angew. Chem., Int. Ed. 2002, 41, 3261. (n) Benson, S. C.; Lee, L.; Snyder, J. K. Tetrahedron Lett. 1996, 37, 5061. (o) Benson, S. C.; Lee, L.; Yang, L.; Snyder, J. K. Tetrahedron 2000, 65, 1165.
24. For IDA reactions in natural product synthesis, see: (a) Boger, D. L.; Honda, T.; Menezes, R. F.; Colletti, S. L. J. Am. Chem. Soc. 1994, 116, 5631. (b) Boger, D. L.; Honda, T.; Dang, Q. J. Am. Chem. Soc. 1994, 116, 5619. (c) Boger, D. L.; Colletti, S. L.; Honda, T.; Menezes, R. F. J. Am. Chem. Soc. 1994, 116, 5607. (d) Boger, D. L.; Menezes, R. F.; Honda, T. Angew. Chem., Int. Ed. Engl. 1993, 32, 273. (e) Boger, D. L.; Menezes, R. F.; Dang, Q. J. Org. Chem. 1992, 57, 4333. (f) Boger, D. L.; Menezes, R. F.; Dang, Q.; Yang, W. BioMed. Chem. Lett. 1992, 2, 261. (g) For related studies, see: Boger, D. L.; Kochanny, M. J. Org. Chem. 1994, 59, 4950. (h) Desimoni, G.; Tacconi, G.; Barco, A.; Pollini, G. P. Natural Product Synthesis through Pericyclic Reactions; ACS Monograph 180; American Chemical Society: Washington, DC, 1983. (i) Davies, D. E.; Gilchrist, T. L.; Roberts, T. G. J. Chem. Soc., Perkin Trans. 1 1983, 1275. (j) Schmidt R. R.; Maier, M. Tetrahedron Lett. 1982, 23, 1789. (k) Desimoni, G.; Tacconi, G. Chem. Rev. 1975, 75, 651 (l) Bodwell, G. J.; Li, J. Org. Lett. 2002, 4, 127. (m) Bodwell, G. J.; Li, J. Angew. Chem., Int. Ed. 2002, 41, 3261. (n) Benson, S. C.; Lee, L.; Snyder, J. K. Tetrahedron Lett. 1996, 37, 5061. (o) Benson, S. C.; Lee, L.; Yang, L.; Snyder, J. K. Tetrahedron 2000, 65, 1165.
25. For IDA reactions in natural product synthesis, see: (a) Boger, D. L.; Honda, T.; Menezes, R. F.; Colletti, S. L. J. Am. Chem. Soc. 1994, 116, 5631. (b) Boger, D. L.; Honda, T.; Dang, Q. J. Am. Chem. Soc. 1994, 116, 5619. (c) Boger, D. L.; Colletti, S. L.; Honda, T.; Menezes, R. F. J. Am. Chem. Soc. 1994, 116, 5607. (d) Boger, D. L.; Menezes, R. F.; Honda, T. Angew. Chem., Int. Ed. Engl. 1993, 32, 273. (e) Boger, D. L.; Menezes, R. F.; Dang, Q. J. Org. Chem. 1992, 57, 4333. (f) Boger, D. L.; Menezes, R. F.; Dang, Q.; Yang, W. BioMed. Chem. Lett. 1992, 2, 261. (g) For related studies, see: Boger, D. L.; Kochanny, M. J. Org. Chem. 1994, 59, 4950. (h) Desimoni, G.; Tacconi, G.; Barco, A.; Pollini, G. P. Natural Product Synthesis through Pericyclic Reactions; ACS Monograph 180; American Chemical Society: Washington, DC, 1983. (i) Davies, D. E.; Gilchrist, T. L.; Roberts, T. G. J. Chem. Soc., Perkin Trans. 1 1983, 1275. (j) Schmidt R. R.; Maier, M. Tetrahedron Lett. 1982, 23, 1789. (k) Desimoni, G.; Tacconi, G. Chem. Rev. 1975, 75, 651 (l) Bodwell, G. J.; Li, J. Org. Lett. 2002, 4, 127. (m) Bodwell, G. J.; Li, J. Angew. Chem., Int. Ed. 2002, 41, 3261. (n) Benson, S. C.; Lee, L.; Snyder, J. K. Tetrahedron Lett. 1996, 37, 5061. (o) Benson, S. C.; Lee, L.; Yang, L.; Snyder, J. K. Tetrahedron 2000, 65, 1165.
26. For IDA reactions in natural product synthesis, see: (a) Boger, D. L.; Honda, T.; Menezes, R. F.; Colletti, S. L. J. Am. Chem. Soc. 1994, 116, 5631. (b) Boger, D. L.; Honda, T.; Dang, Q. J. Am. Chem. Soc. 1994, 116, 5619. (c) Boger, D. L.; Colletti, S. L.; Honda, T.; Menezes, R. F. J. Am. Chem. Soc. 1994, 116, 5607. (d) Boger, D. L.; Menezes, R. F.; Honda, T. Angew. Chem., Int. Ed. Engl. 1993, 32, 273. (e) Boger, D. L.; Menezes, R. F.; Dang, Q. J. Org. Chem. 1992, 57, 4333. (f) Boger, D. L.; Menezes, R. F.; Dang, Q.; Yang, W. BioMed. Chem. Lett. 1992, 2, 261. (g) For related studies, see: Boger, D. L.; Kochanny, M. J. Org. Chem. 1994, 59, 4950. (h) Desimoni, G.; Tacconi, G.; Barco, A.; Pollini, G. P. Natural Product Synthesis through Pericyclic Reactions; ACS Monograph 180; American Chemical Society: Washington, DC, 1983. (i) Davies, D. E.; Gilchrist, T. L.; Roberts, T. G. J. Chem. Soc., Perkin Trans. 1 1983, 1275. (j) Schmidt R. R.; Maier, M. Tetrahedron Lett. 1982, 23, 1789. (k) Desimoni, G.; Tacconi, G. Chem. Rev. 1975, 75, 651 (l) Bodwell, G. J.; Li, J. Org. Lett. 2002, 4, 127. (m) Bodwell, G. J.; Li, J. Angew. Chem., Int. Ed. 2002, 41, 3261. (n) Benson, S. C.; Lee, L.; Snyder, J. K. Tetrahedron Lett. 1996, 37, 5061. (o) Benson, S. C.; Lee, L.; Yang, L.; Snyder, J. K. Tetrahedron 2000, 65, 1165.
27. For IDA reactions in natural product synthesis, see: (a) Boger, D. L.; Honda, T.; Menezes, R. F.; Colletti, S. L. J. Am. Chem. Soc. 1994, 116, 5631. (b) Boger, D. L.; Honda, T.; Dang, Q. J. Am. Chem. Soc. 1994, 116, 5619. (c) Boger, D. L.; Colletti, S. L.; Honda, T.; Menezes, R. F. J. Am. Chem. Soc. 1994, 116, 5607. (d) Boger, D. L.; Menezes, R. F.; Honda, T. Angew. Chem., Int. Ed. Engl. 1993, 32, 273. (e) Boger, D. L.; Menezes, R. F.; Dang, Q. J. Org. Chem. 1992, 57, 4333. (f) Boger, D. L.; Menezes, R. F.; Dang, Q.; Yang, W. BioMed. Chem. Lett. 1992, 2, 261. (g) For related studies, see: Boger, D. L.; Kochanny, M. J. Org. Chem. 1994, 59, 4950. (h) Desimoni, G.; Tacconi, G.; Barco, A.; Pollini, G. P. Natural Product Synthesis through Pericyclic Reactions; ACS Monograph 180; American Chemical Society: Washington, DC, 1983. (i) Davies, D. E.; Gilchrist, T. L.; Roberts, T. G. J. Chem. Soc., Perkin Trans. 1 1983, 1275. (j) Schmidt R. R.; Maier, M. Tetrahedron Lett. 1982, 23, 1789. (k) Desimoni, G.; Tacconi, G. Chem. Rev. 1975, 75, 651 (l) Bodwell, G. J.; Li, J. Org. Lett. 2002, 4, 127. (m) Bodwell, G. J.; Li, J. Angew. Chem., Int. Ed. 2002, 41, 3261. (n) Benson, S. C.; Lee, L.; Snyder, J. K. Tetrahedron Lett. 1996, 37, 5061. (o) Benson, S. C.; Lee, L.; Yang, L.; Snyder, J. K. Tetrahedron 2000, 65, 1165.
28. For IDA reactions in natural product synthesis, see: (a) Boger, D. L.; Honda, T.; Menezes, R. F.; Colletti, S. L. J. Am. Chem. Soc. 1994, 116, 5631. (b) Boger, D. L.; Honda, T.; Dang, Q. J. Am. Chem. Soc. 1994, 116, 5619. (c) Boger, D. L.; Colletti, S. L.; Honda, T.; Menezes, R. F. J. Am. Chem. Soc. 1994, 116, 5607. (d) Boger, D. L.; Menezes, R. F.; Honda, T. Angew. Chem., Int. Ed. Engl. 1993, 32, 273. (e) Boger, D. L.; Menezes, R. F.; Dang, Q. J. Org. Chem. 1992, 57, 4333. (f) Boger, D. L.; Menezes, R. F.; Dang, Q.; Yang, W. BioMed. Chem. Lett. 1992, 2, 261. (g) For related studies, see: Boger, D. L.; Kochanny, M. J. Org. Chem. 1994, 59, 4950. (h) Desimoni, G.; Tacconi, G.; Barco, A.; Pollini, G. P. Natural Product Synthesis through Pericyclic Reactions; ACS Monograph 180; American Chemical Society: Washington, DC, 1983. (i) Davies, D. E.; Gilchrist, T. L.; Roberts, T. G. J. Chem. Soc., Perkin Trans. 1 1983, 1275. (j) Schmidt R. R.; Maier, M. Tetrahedron Lett. 1982, 23, 1789. (k) Desimoni, G.; Tacconi, G. Chem. Rev. 1975, 75, 651 (l) Bodwell, G. J.; Li, J. Org. Lett. 2002, 4, 127. (m) Bodwell, G. J.; Li, J. Angew. Chem., Int. Ed. 2002, 41, 3261. (n) Benson, S. C.; Lee, L.; Snyder, J. K. Tetrahedron Lett. 1996, 37, 5061. (o) Benson, S. C.; Lee, L.; Yang, L.; Snyder, J. K. Tetrahedron 2000, 65, 1165.
29. For IDA reactions in natural product synthesis, see: (a) Boger, D. L.; Honda, T.; Menezes, R. F.; Colletti, S. L. J. Am. Chem. Soc. 1994, 116, 5631. (b) Boger, D. L.; Honda, T.; Dang, Q. J. Am. Chem. Soc. 1994, 116, 5619. (c) Boger, D. L.; Colletti, S. L.; Honda, T.; Menezes, R. F. J. Am. Chem. Soc. 1994, 116, 5607. (d) Boger, D. L.; Menezes, R. F.; Honda, T. Angew. Chem., Int. Ed. Engl. 1993, 32, 273. (e) Boger, D. L.; Menezes, R. F.; Dang, Q. J. Org. Chem. 1992, 57, 4333. (f) Boger, D. L.; Menezes, R. F.; Dang, Q.; Yang, W. BioMed. Chem. Lett. 1992, 2, 261. (g) For related studies, see: Boger, D. L.; Kochanny, M. J. Org. Chem. 1994, 59, 4950. (h) Desimoni, G.; Tacconi, G.; Barco, A.; Pollini, G. P. Natural Product Synthesis through Pericyclic Reactions; ACS Monograph 180; American Chemical Society: Washington, DC, 1983. (i) Davies, D. E.; Gilchrist, T. L.; Roberts, T. G. J. Chem. Soc., Perkin Trans. 1 1983, 1275. (j) Schmidt R. R.; Maier, M. Tetrahedron Lett. 1982, 23, 1789. (k) Desimoni, G.; Tacconi, G. Chem. Rev. 1975, 75, 651 (l) Bodwell, G. J.; Li, J. Org. Lett. 2002, 4, 127. (m) Bodwell, G. J.; Li, J. Angew. Chem., Int. Ed. 2002, 41, 3261. (n) Benson, S. C.; Lee, L.; Snyder, J. K. Tetrahedron Lett. 1996, 37, 5061. (o) Benson, S. C.; Lee, L.; Yang, L.; Snyder, J. K. Tetrahedron 2000, 65, 1165.
30. For IDA reactions in natural product synthesis, see: (a) Boger, D. L.; Honda, T.; Menezes, R. F.; Colletti, S. L. J. Am. Chem. Soc. 1994, 116, 5631. (b) Boger, D. L.; Honda, T.; Dang, Q. J. Am. Chem. Soc. 1994, 116, 5619. (c) Boger, D. L.; Colletti, S. L.; Honda, T.; Menezes, R. F. J. Am. Chem. Soc. 1994, 116, 5607. (d) Boger, D. L.; Menezes, R. F.; Honda, T. Angew. Chem., Int. Ed. Engl. 1993, 32, 273. (e) Boger, D. L.; Menezes, R. F.; Dang, Q. J. Org. Chem. 1992, 57, 4333. (f) Boger, D. L.; Menezes, R. F.; Dang, Q.; Yang, W. BioMed. Chem. Lett. 1992, 2, 261. (g) For related studies, see: Boger, D. L.; Kochanny, M. J. Org. Chem. 1994, 59, 4950. (h) Desimoni, G.; Tacconi, G.; Barco, A.; Pollini, G. P. Natural Product Synthesis through Pericyclic Reactions; ACS Monograph 180; American Chemical Society: Washington, DC, 1983. (i) Davies, D. E.; Gilchrist, T. L.; Roberts, T. G. J. Chem. Soc., Perkin Trans. 1 1983, 1275. (j) Schmidt R. R.; Maier, M. Tetrahedron Lett. 1982, 23, 1789. (k) Desimoni, G.; Tacconi, G. Chem. Rev. 1975, 75, 651 (l) Bodwell, G. J.; Li, J. Org. Lett. 2002, 4, 127. (m) Bodwell, G. J.; Li, J. Angew. Chem., Int. Ed. 2002, 41, 3261. (n) Benson, S. C.; Lee, L.; Snyder, J. K. Tetrahedron Lett. 1996, 37, 5061. (o) Benson, S. C.; Lee, L.; Yang, L.; Snyder, J. K. Tetrahedron 2000, 65, 1165.
31. For IDA reactions in natural product synthesis, see: (a) Boger, D. L.; Honda, T.; Menezes, R. F.; Colletti, S. L. J. Am. Chem. Soc. 1994, 116, 5631. (b) Boger, D. L.; Honda, T.; Dang, Q. J. Am. Chem. Soc. 1994, 116, 5619. (c) Boger, D. L.; Colletti, S. L.; Honda, T.; Menezes, R. F. J. Am. Chem. Soc. 1994, 116, 5607. (d) Boger, D. L.; Menezes, R. F.; Honda, T. Angew. Chem., Int. Ed. Engl. 1993, 32, 273. (e) Boger, D. L.; Menezes, R. F.; Dang, Q. J. Org. Chem. 1992, 57, 4333. (f) Boger, D. L.; Menezes, R. F.; Dang, Q.; Yang, W. BioMed. Chem. Lett. 1992, 2, 261. (g) For related studies, see: Boger, D. L.; Kochanny, M. J. Org. Chem. 1994, 59, 4950. (h) Desimoni, G.; Tacconi, G.; Barco, A.; Pollini, G. P. Natural Product Synthesis through Pericyclic Reactions; ACS Monograph 180; American Chemical Society: Washington, DC, 1983. (i) Davies, D. E.; Gilchrist, T. L.; Roberts, T. G. J. Chem. Soc., Perkin Trans. 1 1983, 1275. (j) Schmidt R. R.; Maier, M. Tetrahedron Lett. 1982, 23, 1789. (k) Desimoni, G.; Tacconi, G. Chem. Rev. 1975, 75, 651 (l) Bodwell, G. J.; Li, J. Org. Lett. 2002, 4, 127. (m) Bodwell, G. J.; Li, J. Angew. Chem., Int. Ed. 2002, 41, 3261. (n) Benson, S. C.; Lee, L.; Snyder, J. K. Tetrahedron Lett. 1996, 37, 5061. (o) Benson, S. C.; Lee, L.; Yang, L.; Snyder, J. K. Tetrahedron 2000, 65, 1165.
32. For IDA reactions in natural product synthesis, see: (a) Boger, D. L.; Honda, T.; Menezes, R. F.; Colletti, S. L. J. Am. Chem. Soc. 1994, 116, 5631. (b) Boger, D. L.; Honda, T.; Dang, Q. J. Am. Chem. Soc. 1994, 116, 5619. (c) Boger, D. L.; Colletti, S. L.; Honda, T.; Menezes, R. F. J. Am. Chem. Soc. 1994, 116, 5607. (d) Boger, D. L.; Menezes, R. F.; Honda, T. Angew. Chem., Int. Ed. Engl. 1993, 32, 273. (e) Boger, D. L.; Menezes, R. F.; Dang, Q. J. Org. Chem. 1992, 57, 4333. (f) Boger, D. L.; Menezes, R. F.; Dang, Q.; Yang, W. BioMed. Chem. Lett. 1992, 2, 261. (g) For related studies, see: Boger, D. L.; Kochanny, M. J. Org. Chem. 1994, 59, 4950. (h) Desimoni, G.; Tacconi, G.; Barco, A.; Pollini, G. P. Natural Product Synthesis through Pericyclic Reactions; ACS Monograph 180; American Chemical Society: Washington, DC, 1983. (i) Davies, D. E.; Gilchrist, T. L.; Roberts, T. G. J. Chem. Soc., Perkin Trans. 1 1983, 1275. (j) Schmidt R. R.; Maier, M. Tetrahedron Lett. 1982, 23, 1789. (k) Desimoni, G.; Tacconi, G. Chem. Rev. 1975, 75, 651 (l) Bodwell, G. J.; Li, J. Org. Lett. 2002, 4, 127. (m) Bodwell, G. J.; Li, J. Angew. Chem., Int. Ed. 2002, 41, 3261. (n) Benson, S. C.; Lee, L.; Snyder, J. K. Tetrahedron Lett. 1996, 37, 5061. (o) Benson, S. C.; Lee, L.; Yang, L.; Snyder, J. K. Tetrahedron 2000, 65, 1165.
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63. For discussions of theoretical studies of elimination reactions, see: (a) Ensing, B.; Laio, A.; Gervasio, F.; Parrinello, M.; Klein, M. J. Am. Chem. Soc. 2004, 126, 9492. (b) Minato, T.; Yamabe, S. J. Am. Chem. Soc. 1988, 110, 4586. (c) Bickelhaupt, F. M.; Baerends, E. J.; Nibbering, N. M. M.; Ziegler, T. J. Am. Chem. Soc. 1993, 115, 9160. (d) Merril, G. N.; Gronert, S.; Kass, S. R. J. Phys. Chem. A 1997, 101, 208. (e) Glad, S. S.; Jensen, F. J. Org. Chem. 1997, 62, 253. (f) Mugnai, M.; Cardini, G.; Schettino, V. J. Phys. Chem. A 2003, 107, 2540. (g) Mertell, J. M.; Beaton, P. T.; Holmes, B. E. J. Phys. Chem. A 2002, 106, 8471. (h) Kato, S.; Morokuma, K. J. Chem. Phys. 1980, 73, 3900. (i) Hu, W.-P.; Truhlar, D. G. J. Am. Chem. Soc. 1996, 118, 860. (j) Hiberty, P. C. J. Am. Chem. Soc. 1975, 97, 5975.
64. For discussions of theoretical studies of elimination reactions, see: (a) Ensing, B.; Laio, A.; Gervasio, F.; Parrinello, M.; Klein, M. J. Am. Chem. Soc. 2004, 126, 9492. (b) Minato, T.; Yamabe, S. J. Am. Chem. Soc. 1988, 110, 4586. (c) Bickelhaupt, F. M.; Baerends, E. J.; Nibbering, N. M. M.; Ziegler, T. J. Am. Chem. Soc. 1993, 115, 9160. (d) Merril, G. N.; Gronert, S.; Kass, S. R. J. Phys. Chem. A 1997, 101, 208. (e) Glad, S. S.; Jensen, F. J. Org. Chem. 1997, 62, 253. (f) Mugnai, M.; Cardini, G.; Schettino, V. J. Phys. Chem. A 2003, 107, 2540. (g) Mertell, J. M.; Beaton, P. T.; Holmes, B. E. J. Phys. Chem. A 2002, 106, 8471. (h) Kato, S.; Morokuma, K. J. Chem. Phys. 1980, 73, 3900. (i) Hu, W.-P.; Truhlar, D. G. J. Am. Chem. Soc. 1996, 118, 860. (j) Hiberty, P. C. J. Am. Chem. Soc. 1975, 97, 5975.
65. For discussions of theoretical studies of elimination reactions, see: (a) Ensing, B.; Laio, A.; Gervasio, F.; Parrinello, M.; Klein, M. J. Am. Chem. Soc. 2004, 126, 9492. (b) Minato, T.; Yamabe, S. J. Am. Chem. Soc. 1988, 110, 4586. (c) Bickelhaupt, F. M.; Baerends, E. J.; Nibbering, N. M. M.; Ziegler, T. J. Am. Chem. Soc. 1993, 115, 9160. (d) Merril, G. N.; Gronert, S.; Kass, S. R. J. Phys. Chem. A 1997, 101, 208. (e) Glad, S. S.; Jensen, F. J. Org. Chem. 1997, 62, 253. (f) Mugnai, M.; Cardini, G.; Schettino, V. J. Phys. Chem. A 2003, 107, 2540. (g) Mertell, J. M.; Beaton, P. T.; Holmes, B. E. J. Phys. Chem. A 2002, 106, 8471. (h) Kato, S.; Morokuma, K. J. Chem. Phys. 1980, 73, 3900. (i) Hu, W.-P.; Truhlar, D. G. J. Am. Chem. Soc. 1996, 118, 860. (j) Hiberty, P. C. J. Am. Chem. Soc. 1975, 97, 5975.
66. For discussions of theoretical studies of elimination reactions, see: (a) Ensing, B.; Laio, A.; Gervasio, F.; Parrinello, M.; Klein, M. J. Am. Chem. Soc. 2004, 126, 9492. (b) Minato, T.; Yamabe, S. J. Am. Chem. Soc. 1988, 110, 4586. (c) Bickelhaupt, F. M.; Baerends, E. J.; Nibbering, N. M. M.; Ziegler, T. J. Am. Chem. Soc. 1993, 115, 9160. (d) Merril, G. N.; Gronert, S.; Kass, S. R. J. Phys. Chem. A 1997, 101, 208. (e) Glad, S. S.; Jensen, F. J. Org. Chem. 1997, 62, 253. (f) Mugnai, M.; Cardini, G.; Schettino, V. J. Phys. Chem. A 2003, 107, 2540. (g) Mertell, J. M.; Beaton, P. T.; Holmes, B. E. J. Phys. Chem. A 2002, 106, 8471. (h) Kato, S.; Morokuma, K. J. Chem. Phys. 1980, 73, 3900. (i) Hu, W.-P.; Truhlar, D. G. J. Am. Chem. Soc. 1996, 118, 860. (j) Hiberty, P. C. J. Am. Chem. Soc. 1975, 97, 5975.
67. For discussions of theoretical studies of elimination reactions, see: (a) Ensing, B.; Laio, A.; Gervasio, F.; Parrinello, M.; Klein, M. J. Am. Chem. Soc. 2004, 126, 9492. (b) Minato, T.; Yamabe, S. J. Am. Chem. Soc. 1988, 110, 4586. (c) Bickelhaupt, F. M.; Baerends, E. J.; Nibbering, N. M. M.; Ziegler, T. J. Am. Chem. Soc. 1993, 115, 9160. (d) Merril, G. N.; Gronert, S.; Kass, S. R. J. Phys. Chem. A 1997, 101, 208. (e) Glad, S. S.; Jensen, F. J. Org. Chem. 1997, 62, 253. (f) Mugnai, M.; Cardini, G.; Schettino, V. J. Phys. Chem. A 2003, 107, 2540. (g) Mertell, J. M.; Beaton, P. T.; Holmes, B. E. J. Phys. Chem. A 2002, 106, 8471. (h) Kato, S.; Morokuma, K. J. Chem. Phys. 1980, 73, 3900. (i) Hu, W.-P.; Truhlar, D. G. J. Am. Chem. Soc. 1996, 118, 860. (j) Hiberty, P. C. J. Am. Chem. Soc. 1975, 97, 5975.
68. For discussions of theoretical studies of elimination reactions, see: (a) Ensing, B.; Laio, A.; Gervasio, F.; Parrinello, M.; Klein, M. J. Am. Chem. Soc. 2004, 126, 9492. (b) Minato, T.; Yamabe, S. J. Am. Chem. Soc. 1988, 110, 4586. (c) Bickelhaupt, F. M.; Baerends, E. J.; Nibbering, N. M. M.; Ziegler, T. J. Am. Chem. Soc. 1993, 115, 9160. (d) Merril, G. N.; Gronert, S.; Kass, S. R. J. Phys. Chem. A 1997, 101, 208. (e) Glad, S. S.; Jensen, F. J. Org. Chem. 1997, 62, 253. (f) Mugnai, M.; Cardini, G.; Schettino, V. J. Phys. Chem. A 2003, 107, 2540. (g) Mertell, J. M.; Beaton, P. T.; Holmes, B. E. J. Phys. Chem. A 2002, 106, 8471. (h) Kato, S.; Morokuma, K. J. Chem. Phys. 1980, 73, 3900. (i) Hu, W.-P.; Truhlar, D. G. J. Am. Chem. Soc. 1996, 118, 860. (j) Hiberty, P. C. J. Am. Chem. Soc. 1975, 97, 5975.
69. For discussions of theoretical studies of elimination reactions, see: (a) Ensing, B.; Laio, A.; Gervasio, F.; Parrinello, M.; Klein, M. J. Am. Chem. Soc. 2004, 126, 9492. (b) Minato, T.; Yamabe, S. J. Am. Chem. Soc. 1988, 110, 4586. (c) Bickelhaupt, F. M.; Baerends, E. J.; Nibbering, N. M. M.; Ziegler, T. J. Am. Chem. Soc. 1993, 115, 9160. (d) Merril, G. N.; Gronert, S.; Kass, S. R. J. Phys. Chem. A 1997, 101, 208. (e) Glad, S. S.; Jensen, F. J. Org. Chem. 1997, 62, 253. (f) Mugnai, M.; Cardini, G.; Schettino, V. J. Phys. Chem. A 2003, 107, 2540. (g) Mertell, J. M.; Beaton, P. T.; Holmes, B. E. J. Phys. Chem. A 2002, 106, 8471. (h) Kato, S.; Morokuma, K. J. Chem. Phys. 1980, 73, 3900. (i) Hu, W.-P.; Truhlar, D. G. J. Am. Chem. Soc. 1996, 118, 860. (j) Hiberty, P. C. J. Am. Chem. Soc. 1975, 97, 5975.
70. For discussions of theoretical studies of elimination reactions, see: (a) Ensing, B.; Laio, A.; Gervasio, F.; Parrinello, M.; Klein, M. J. Am. Chem. Soc. 2004, 126, 9492. (b) Minato, T.; Yamabe, S. J. Am. Chem. Soc. 1988, 110, 4586. (c) Bickelhaupt, F. M.; Baerends, E. J.; Nibbering, N. M. M.; Ziegler, T. J. Am. Chem. Soc. 1993, 115, 9160. (d) Merril, G. N.; Gronert, S.; Kass, S. R. J. Phys. Chem. A 1997, 101, 208. (e) Glad, S. S.; Jensen, F. J. Org. Chem. 1997, 62, 253. (f) Mugnai, M.; Cardini, G.; Schettino, V. J. Phys. Chem. A 2003, 107, 2540. (g) Mertell, J. M.; Beaton, P. T.; Holmes, B. E. J. Phys. Chem. A 2002, 106, 8471. (h) Kato, S.; Morokuma, K. J. Chem. Phys. 1980, 73, 3900. (i) Hu, W.-P.; Truhlar, D. G. J. Am. Chem. Soc. 1996, 118, 860. (j) Hiberty, P. C. J. Am. Chem. Soc. 1975, 97, 5975.
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77. 5 it has been found that addition of acids in some reactions has little effect on the reaction rate, suggesting that the elimination of ammonia is not rate-determining.
78. The different reactivity of the aromatic heterocycles is attributed to their different aromaticity (unpublished results). For discussions of aromaticity in different heterocycles, see: (a) Katritzky, A. R.; Karelson, M.; Sild, S.; Krygowski, T. M.; Jug, K. J. Org. Chem. 1998, 63, 5228. (b) Cyranski, M.; Krygowski, T. M.; Katritzky, A. R.; Schleyer, P. v. R. J. Org. Chem. 2002, 67, 1333. For discussions of effects of product aromaticity on the lowering of barrier heights, see: (c) Birney, D, M.; Berson, J. A. Tetrahedron 1986, 42, 1561. (d) Braun, R.; Kummer, M.; Martin, H.-D.; Rubin, M. B. Angew. Chem., Int. Ed. Engl. 1985, 24, 1059. (e) Bertsch, A.; Grimme, W.; Reinhardt, G. Angew. Chem., Int. Ed. Engl. 1986, 25, 377. (f) Bearpark, M.; Bernaidyi, F.; Olivucci, M.; Robb, M. A. J. Am. Chem. Soc. 1990, 112, 1732. (g) Bernardi, F.; Celani, P.; Olivucci, M.; Robb, M. A.; Suzzi-Valli, G. J. Am. Chem. Soc. 1995, 117, 10531. For the Bell-Evans-Polanyi principle, see: (h) Dewar, M. J. S. The Molecular Orbital Theory for Organic Chemistry; McGraw-Hill: New York, 1969. (i) Dewar, M. J. S. J. Am. Chem. Soc. 1984, 106, 209.
79. The different reactivity of the aromatic heterocycles is attributed to their different aromaticity (unpublished results). For discussions of aromaticity in different heterocycles, see: (a) Katritzky, A. R.; Karelson, M.; Sild, S.; Krygowski, T. M.; Jug, K. J. Org. Chem. 1998, 63, 5228. (b) Cyranski, M.; Krygowski, T. M.; Katritzky, A. R.; Schleyer, P. v. R. J. Org. Chem. 2002, 67, 1333. For discussions of effects of product aromaticity on the lowering of barrier heights, see: (c) Birney, D, M.; Berson, J. A. Tetrahedron 1986, 42, 1561. (d) Braun, R.; Kummer, M.; Martin, H.-D.; Rubin, M. B. Angew. Chem., Int. Ed. Engl. 1985, 24, 1059. (e) Bertsch, A.; Grimme, W.; Reinhardt, G. Angew. Chem., Int. Ed. Engl. 1986, 25, 377. (f) Bearpark, M.; Bernaidyi, F.; Olivucci, M.; Robb, M. A. J. Am. Chem. Soc. 1990, 112, 1732. (g) Bernardi, F.; Celani, P.; Olivucci, M.; Robb, M. A.; Suzzi-Valli, G. J. Am. Chem. Soc. 1995, 117, 10531. For the Bell-Evans-Polanyi principle, see: (h) Dewar, M. J. S. The Molecular Orbital Theory for Organic Chemistry; McGraw-Hill: New York, 1969. (i) Dewar, M. J. S. J. Am. Chem. Soc. 1984, 106, 209.
80. The different reactivity of the aromatic heterocycles is attributed to their different aromaticity (unpublished results). For discussions of aromaticity in different heterocycles, see: (a) Katritzky, A. R.; Karelson, M.; Sild, S.; Krygowski, T. M.; Jug, K. J. Org. Chem. 1998, 63, 5228. (b) Cyranski, M.; Krygowski, T. M.; Katritzky, A. R.; Schleyer, P. v. R. J. Org. Chem. 2002, 67, 1333. For discussions of effects of product aromaticity on the lowering of barrier heights, see: (c) Birney, D, M.; Berson, J. A. Tetrahedron 1986, 42, 1561. (d) Braun, R.; Kummer, M.; Martin, H.-D.; Rubin, M. B. Angew. Chem., Int. Ed. Engl. 1985, 24, 1059. (e) Bertsch, A.; Grimme, W.; Reinhardt, G. Angew. Chem., Int. Ed. Engl. 1986, 25, 377. (f) Bearpark, M.; Bernaidyi, F.; Olivucci, M.; Robb, M. A. J. Am. Chem. Soc. 1990, 112, 1732. (g) Bernardi, F.; Celani, P.; Olivucci, M.; Robb, M. A.; Suzzi-Valli, G. J. Am. Chem. Soc. 1995, 117, 10531. For the Bell-Evans-Polanyi principle, see: (h) Dewar, M. J. S. The Molecular Orbital Theory for Organic Chemistry; McGraw-Hill: New York, 1969. (i) Dewar, M. J. S. J. Am. Chem. Soc. 1984, 106, 209.
81. The different reactivity of the aromatic heterocycles is attributed to their different aromaticity (unpublished results). For discussions of aromaticity in different heterocycles, see: (a) Katritzky, A. R.; Karelson, M.; Sild, S.; Krygowski, T. M.; Jug, K. J. Org. Chem. 1998, 63, 5228. (b) Cyranski, M.; Krygowski, T. M.; Katritzky, A. R.; Schleyer, P. v. R. J. Org. Chem. 2002, 67, 1333. For discussions of effects of product aromaticity on the lowering of barrier heights, see: (c) Birney, D, M.; Berson, J. A. Tetrahedron 1986, 42, 1561. (d) Braun, R.; Kummer, M.; Martin, H.-D.; Rubin, M. B. Angew. Chem., Int. Ed. Engl. 1985, 24, 1059. (e) Bertsch, A.; Grimme, W.; Reinhardt, G. Angew. Chem., Int. Ed. Engl. 1986, 25, 377. (f) Bearpark, M.; Bernaidyi, F.; Olivucci, M.; Robb, M. A. J. Am. Chem. Soc. 1990, 112, 1732. (g) Bernardi, F.; Celani, P.; Olivucci, M.; Robb, M. A.; Suzzi-Valli, G. J. Am. Chem. Soc. 1995, 117, 10531. For the Bell-Evans-Polanyi principle, see: (h) Dewar, M. J. S. The Molecular Orbital Theory for Organic Chemistry; McGraw-Hill: New York, 1969. (i) Dewar, M. J. S. J. Am. Chem. Soc. 1984, 106, 209.
82. The different reactivity of the aromatic heterocycles is attributed to their different aromaticity (unpublished results). For discussions of aromaticity in different heterocycles, see: (a) Katritzky, A. R.; Karelson, M.; Sild, S.; Krygowski, T. M.; Jug, K. J. Org. Chem. 1998, 63, 5228. (b) Cyranski, M.; Krygowski, T. M.; Katritzky, A. R.; Schleyer, P. v. R. J. Org. Chem. 2002, 67, 1333. For discussions of effects of product aromaticity on the lowering of barrier heights, see: (c) Birney, D, M.; Berson, J. A. Tetrahedron 1986, 42, 1561. (d) Braun, R.; Kummer, M.; Martin, H.-D.; Rubin, M. B. Angew. Chem., Int. Ed. Engl. 1985, 24, 1059. (e) Bertsch, A.; Grimme, W.; Reinhardt, G. Angew. Chem., Int. Ed. Engl. 1986, 25, 377. (f) Bearpark, M.; Bernaidyi, F.; Olivucci, M.; Robb, M. A. J. Am. Chem. Soc. 1990, 112, 1732. (g) Bernardi, F.; Celani, P.; Olivucci, M.; Robb, M. A.; Suzzi-Valli, G. J. Am. Chem. Soc. 1995, 117, 10531. For the Bell-Evans-Polanyi principle, see: (h) Dewar, M. J. S. The Molecular Orbital Theory for Organic Chemistry; McGraw-Hill: New York, 1969. (i) Dewar, M. J. S. J. Am. Chem. Soc. 1984, 106, 209.
83. The different reactivity of the aromatic heterocycles is attributed to their different aromaticity (unpublished results). For discussions of aromaticity in different heterocycles, see: (a) Katritzky, A. R.; Karelson, M.; Sild, S.; Krygowski, T. M.; Jug, K. J. Org. Chem. 1998, 63, 5228. (b) Cyranski, M.; Krygowski, T. M.; Katritzky, A. R.; Schleyer, P. v. R. J. Org. Chem. 2002, 67, 1333. For discussions of effects of product aromaticity on the lowering of barrier heights, see: (c) Birney, D, M.; Berson, J. A. Tetrahedron 1986, 42, 1561. (d) Braun, R.; Kummer, M.; Martin, H.-D.; Rubin, M. B. Angew. Chem., Int. Ed. Engl. 1985, 24, 1059. (e) Bertsch, A.; Grimme, W.; Reinhardt, G. Angew. Chem., Int. Ed. Engl. 1986, 25, 377. (f) Bearpark, M.; Bernaidyi, F.; Olivucci, M.; Robb, M. A. J. Am. Chem. Soc. 1990, 112, 1732. (g) Bernardi, F.; Celani, P.; Olivucci, M.; Robb, M. A.; Suzzi-Valli, G. J. Am. Chem. Soc. 1995, 117, 10531. For the Bell-Evans-Polanyi principle, see: (h) Dewar, M. J. S. The Molecular Orbital Theory for Organic Chemistry; McGraw-Hill: New York, 1969. (i) Dewar, M. J. S. J. Am. Chem. Soc. 1984, 106, 209.
84. The different reactivity of the aromatic heterocycles is attributed to their different aromaticity (unpublished results). For discussions of aromaticity in different heterocycles, see: (a) Katritzky, A. R.; Karelson, M.; Sild, S.; Krygowski, T. M.; Jug, K. J. Org. Chem. 1998, 63, 5228. (b) Cyranski, M.; Krygowski, T. M.; Katritzky, A. R.; Schleyer, P. v. R. J. Org. Chem. 2002, 67, 1333. For discussions of effects of product aromaticity on the lowering of barrier heights, see: (c) Birney, D, M.; Berson, J. A. Tetrahedron 1986, 42, 1561. (d) Braun, R.; Kummer, M.; Martin, H.-D.; Rubin, M. B. Angew. Chem., Int. Ed. Engl. 1985, 24, 1059. (e) Bertsch, A.; Grimme, W.; Reinhardt, G. Angew. Chem., Int. Ed. Engl. 1986, 25, 377. (f) Bearpark, M.; Bernaidyi, F.; Olivucci, M.; Robb, M. A. J. Am. Chem. Soc. 1990, 112, 1732. (g) Bernardi, F.; Celani, P.; Olivucci, M.; Robb, M. A.; Suzzi-Valli, G. J. Am. Chem. Soc. 1995, 117, 10531. For the Bell-Evans-Polanyi principle, see: (h) Dewar, M. J. S. The Molecular Orbital Theory for Organic Chemistry; McGraw-Hill: New York, 1969. (i) Dewar, M. J. S. J. Am. Chem. Soc. 1984, 106, 209.
85. The different reactivity of the aromatic heterocycles is attributed to their different aromaticity (unpublished results). For discussions of aromaticity in different heterocycles, see: (a) Katritzky, A. R.; Karelson, M.; Sild, S.; Krygowski, T. M.; Jug, K. J. Org. Chem. 1998, 63, 5228. (b) Cyranski, M.; Krygowski, T. M.; Katritzky, A. R.; Schleyer, P. v. R. J. Org. Chem. 2002, 67, 1333. For discussions of effects of product aromaticity on the lowering of barrier heights, see: (c) Birney, D, M.; Berson, J. A. Tetrahedron 1986, 42, 1561. (d) Braun, R.; Kummer, M.; Martin, H.-D.; Rubin, M. B. Angew. Chem., Int. Ed. Engl. 1985, 24, 1059. (e) Bertsch, A.; Grimme, W.; Reinhardt, G. Angew. Chem., Int. Ed. Engl. 1986, 25, 377. (f) Bearpark, M.; Bernaidyi, F.; Olivucci, M.; Robb, M. A. J. Am. Chem. Soc. 1990, 112, 1732. (g) Bernardi, F.; Celani, P.; Olivucci, M.; Robb, M. A.; Suzzi-Valli, G. J. Am. Chem. Soc. 1995, 117, 10531. For the Bell-Evans-Polanyi principle, see: (h) Dewar, M. J. S. The Molecular Orbital Theory for Organic Chemistry; McGraw-Hill: New York, 1969. (i) Dewar, M. J. S. J. Am. Chem. Soc. 1984, 106, 209.
86. The different reactivity of the aromatic heterocycles is attributed to their different aromaticity (unpublished results). For discussions of aromaticity in different heterocycles, see: (a) Katritzky, A. R.; Karelson, M.; Sild, S.; Krygowski, T. M.; Jug, K. J. Org. Chem. 1998, 63, 5228. (b) Cyranski, M.; Krygowski, T. M.; Katritzky, A. R.; Schleyer, P. v. R. J. Org. Chem. 2002, 67, 1333. For discussions of effects of product aromaticity on the lowering of barrier heights, see: (c) Birney, D, M.; Berson, J. A. Tetrahedron 1986, 42, 1561. (d) Braun, R.; Kummer, M.; Martin, H.-D.; Rubin, M. B. Angew. Chem., Int. Ed. Engl. 1985, 24, 1059. (e) Bertsch, A.; Grimme, W.; Reinhardt, G. Angew. Chem., Int. Ed. Engl. 1986, 25, 377. (f) Bearpark, M.; Bernaidyi, F.; Olivucci, M.; Robb, M. A. J. Am. Chem. Soc. 1990, 112, 1732. (g) Bernardi, F.; Celani, P.; Olivucci, M.; Robb, M. A.; Suzzi-Valli, G. J. Am. Chem. Soc. 1995, 117, 10531. For the Bell-Evans-Polanyi principle, see: (h) Dewar, M. J. S. The Molecular Orbital Theory for Organic Chemistry; McGraw-Hill: New York, 1969. (i) Dewar, M. J. S. J. Am. Chem. Soc. 1984, 106, 209.
87. (a) Schleyer, P. von R.; Maerker, C.; Dransfeld, A.; Jiao, H.; Hommes, N. J. R. v. E. J. Am. Chem. Soc. 1996, 118, 6317.
88. (b) Manoharan, M.; Proft, F. D.; Geerlings, P. J. Org. Chem. 2000, 65, 7971.
89. Reported NICS values in this paper were computed using the keyword "NMR" in Gaussian 98. The NICS values computed here are smaller than that of the (3 + 2) transition state (see: Cossio, F. P.; Morao, I.; Jiao, H.; Schleyer, P. v. R. J. Am. Chem. Soc. 1999, 121, 6737). The different NICSs values for the (4 + 2) and (3 + 2) transition states could be attributed to their different geometries (folded vs planar transition states). For discussions of computing aromaticity, see also: (a) Alajarin, M.; Sanchez-Andrada, P.; Cossio, F. P.; Arrieta, A.; Lecea, B. J. Org. Chem. 2001, 66, 8470. (b) Schleyer, P. v. R.; Mancharan, M.; Wang, Z.-X.; Kiran, B.; Jiao, H.; Puchta, R.; Hommes, N. J. R. v. E. Org. Lett. 2001, 3, 2465.
90. Reported NICS values in this paper were computed using the keyword "NMR" in Gaussian 98. The NICS values computed here are smaller than that of the (3 + 2) transition state (see: Cossio, F. P.; Morao, I.; Jiao, H.; Schleyer, P. v. R. J. Am. Chem. Soc. 1999, 121, 6737). The different NICSs values for the (4 + 2) and (3 + 2) transition states could be attributed to their different geometries (folded vs planar transition states). For discussions of computing aromaticity, see also: (a) Alajarin, M.; Sanchez-Andrada, P.; Cossio, F. P.; Arrieta, A.; Lecea, B. J. Org. Chem. 2001, 66, 8470. (b) Schleyer, P. v. R.; Mancharan, M.; Wang, Z.-X.; Kiran, B.; Jiao, H.; Puchta, R.; Hommes, N. J. R. v. E. Org. Lett. 2001, 3, 2465.
91. Reported NICS values in this paper were computed using the keyword "NMR" in Gaussian 98. The NICS values computed here are smaller than that of the (3 + 2) transition state (see: Cossio, F. P.; Morao, I.; Jiao, H.; Schleyer, P. v. R. J. Am. Chem. Soc. 1999, 121, 6737). The different NICSs values for the (4 + 2) and (3 + 2) transition states could be attributed to their different geometries (folded vs planar transition states). For discussions of computing aromaticity, see also: (a) Alajarin, M.; Sanchez-Andrada, P.; Cossio, F. P.; Arrieta, A.; Lecea, B. J. Org. Chem. 2001, 66, 8470. (b) Schleyer, P. v. R.; Mancharan, M.; Wang, Z.-X.; Kiran, B.; Jiao, H.; Puchta, R.; Hommes, N. J. R. v. E. Org. Lett. 2001, 3, 2465.
92. Jacobi, P. A.; Lee, K. J. Am. Chem. Soc. 2000, 122, 4295.
93. Raw, S. A.; Taylor, J. K. J. Am. Chem, Soc, 2004, 126, 12260.