Regioselectivity of radical additions to substituted alkenes: Insight from conceptual density functional theory

Journal of Organic Chemistry

Volumn 75, Issue 15, 2010, Pages 4964-4974

  De Vleeschouwer, Freija ^a   Jaque, Pablo ^b   Geerlings, Paul ^a   Toro Labbé, Alejandro ^c   De Proft, Frank ^a  

^a VRIJE UNIVERSITEIT BRUSSEL   (Belgium)

^b UNIVERSIDAD ANDRÉS BELLO   (Chile)

^c PONTIFICIA UNIVERSIDAD CATÓLICA DE CHILE   (Chile)

Author keywords

[No Author keywords available]

Indexed keywords

ACTIVATION BARRIERS; CHEMICAL CONCEPTS; CONCEPTUAL DENSITY FUNCTIONAL THEORY; DESCRIPTORS; ELECTRON-RICH; INITIAL STAGES; POLAR EFFECT; PRODUCT STABILITY; RADICAL ADDITION; RADICAL CHEMISTRY; REACTIVITY DESCRIPTORS; SPIN-POLARIZED; SUBSTITUTED ALKENE;

DENSITY FUNCTIONAL THEORY; OLEFINS; REGIOSELECTIVITY;

ADDITION REACTIONS;

ALKENE DERIVATIVE; ELECTROPHILE; NUCLEOPHILE; RADICAL;

ADDITION REACTION; ARTICLE; CHEMICAL REACTION; CORRELATION ANALYSIS; DENSITY FUNCTIONAL THEORY; ELECTRON TRANSPORT; NUCLEOPHILICITY; REACTION ANALYSIS; THERMODYNAMICS;

EID: 77955162162     PISSN: 00223263     EISSN: 15206904     Source Type: Journal    
DOI: 10.1021/jo100503e     Document Type: Article

References (47)

1. Tedder, M.; Walton, J. C. Acc. Chem. Res. 1976, 9, 183
2. Tedder, M.; Walton, J. C. Tetrahedron 1980, 36, 701
3. Giese, B. Angew. Chem., Int. Ed. Engl. 1983, 22, 753
4. Münger, K.; Fischer, H. Int. J. Chem. Kinet. 1985, 17, 809
5. Wu, J. Q.; Fischer, H. Int J. Chem. Kinet. 1995, 27, 167
6. Ponec, R.; Malek, J.; Kuhnel, W.; Gey, E. J. Mol. Struct. 1984, 110, 293
7. Delbecq, F.; Ilavsky, D.; Ahn, N. T.; Lefour, J. M. J. Am. Chem. Soc. 1985, 107, 1623
8. Riemenschneider, K.; Bartels, H. M.; Dornow, R.; Drechsel-Grau, E.; Eichel, W.; Luthe, H.; Matter, Y. M.; Michaelis, W.; Boldt, P. J. Org. Chem. 1987, 52, 205
9. Wong, M. W.; Pross, A.; Radom, L. J. Am. Chem. Soc. 1993, 115, 11050
10. Héberger, K.; Fischer, H. Int. J. Chem. Kinet. 1993, 25, 913
11. Héberger, K.; Lopata, A. J. Org. Chem. 1998, 63, 8646
12. Botoni, A. J. Chem. Soc., Perkin Trans. 2 1996, 2041
13. Parr, R. G.; Von Szentpaly, L.; Liu, S. B. J. Am. Chem. Soc. 1999, 121, 1922
14. De Vleeschouwer, F.; Van Speybroeck, V.; Waroquier, M.; Geerlings, P.; De Proft, F. Org. Lett. 2007, 9, 2721
15. De Dobbeleer, C.; Pospiil, J.; De Vleeschouwer, F.; De Proft, F.; Marko, I. E. Chem. Commun. 2009, 2142
16. Takahara, Y.; Iino, M.; Matsuda, M. Bull. Chem. Soc. Jpn. 1976, 49, 2268
17. da Silva Corra, C. M.; M.; Fleming, M. D. C. M.; Oliviera, M.A.B.C.S.; Garrido, E. M. J. J. Chem. Soc., Perkin Trans. 2 1994, 1993
18. Weber, M.; Fischer, H. Helv. Chim. Acta 1998, 81, 770
19. We managed to find transition states for these electrophilic radical addition reactions using the MP2 method, but comparison of reaction data for the addition of the nucleophilic methyl and hydroxymethyl and the neutral cyanomethyl radicals with literature showed that the MP2 method (largely) overestimates the experimental reaction data (see ref 20). The reason that reaction data could be obtained for the larger (in size) phenylsulfonyl, tosyl, and cyclic malonyl radicals is (probably) due to the fact that these radicals are highly stable compared to the hydroxyl and chlorine radicals (see ref 21).
20. Wong, M. W.; Radom, L. J. Phys. Chem. A 1998, 102, 2237
21. De Vleeschouwer, F.; Van Speybroeck, V.; Waroquier, M.; Geerlings, P.; De Proft, F. J. Org. Chem. 2008, 73, 9109
22. Wong, M. W.; Pross, A.; Radom, L. J. Am. Chem. Soc. 1994, 116, 6284
23. Geerlings, P.; De Proft, F.; Langenaeker, W. Chem. Rev. 2003, 103, 1793
24. Geerlings, P.; De Proft, F. Phys. Chem. Chem. Phys. 2008, 10, 3028
25. Lalevée, J.; Allonas, X.; Fouassier, J. P.; Rinaldi, D.; Ruiz Lopez, M. F.; Rivail, J. L. Chem. Phys. Lett. 2005, 415, 202
26. Politzer, P.; Toro-Labbé, A.; Gutiérrez-Oliva, S.; Herrera, B.; Jaque, P.; Concha, M. C.; Murray, J. S. J. Chem. Sci. 2005, 117, 467
27. Burda, J. V.; Toro-Labbé, A.; Gutiérrez-Oliva, S.; Murray, J. S.; Politzer, P. J. Phys. Chem. A 2007, 111, 2455
28. Morell, C.; Grand, A.; Gutiérrez-Oliva, S.; Toro-Labbé, A. In Theoretical Aspects of Chemical Reactivity; Toro-Labbé, A., Ed.; Elsevier: Amsterdam, 2004; p 101.
29. De Vleeschouwer, F.; Toro-Labbé, A.; Gutiérez-Oliva, S.; Van Speybroeck, V.; Waroquier, M.; Geerlings, P.; De Proft, F. J. Phys. Chem. A 2009, 113, 7899
30. Arnaud, R.; Subra, R.; Barone, V.; Lelj, F.; Olivella, S.; Sole, A.; Russo, N. J. Chem. Soc. Perkin Trans. 2 1986, 1517
31. Zipse, H.; He, J.; Houk, K. N.; Giese, B J. Am. Chem. Soc. 1991, 113, 4324
32. Reed, A. E.; Weinhold, F. J. Chem. Phys. 1985, 83, 1736
33. Reed, A. E.; Weinstock, R. B.; Weinhold, F. J. Chem. Phys. 1985, 83, 735
34. Reed, A. E.; Curtiss, L. A.; Weinhold, F. Chem. Rev. 1988, 88, 899
35. Parr, R. G.; Pearson, R. G. J. Am. Chem. Soc. 1983, 105, 7512
36. De Vleeschouwer, F.; De Proft, F.; Geerlings, P. J. Mol. Struct. (Theochem) 2010, 943, 94.
37. De Proft, F.; Chamorro, E.; Pérez, P.; Duque, M.; De Vleeschouwer, F.; Geerlings, P. Specialist Periodical Reports: Chemical Modeling: Applications and Theory; Springborg, M., Ed.; Royal Society of Chemistry: Cambridge, UK, 2009; Vol. 6, pp 63 - 111.
38. Morell, C.; Grand, A.; Toro-Labbé, A. J. Phys. Chem. A 2005, 109, 205
39. Chamorro, E.; Pérez, P.; Duque, M.; De Proft, F.; Geerlings, P. J. Chem. Phys. 2008, 129, 064117
40. Galvan, M.; Vela, A.; Gazquez, J. L. J. Phys. Chem. 1988, 92, 6470
41. Ayers, P.; Morell, C.; De Proft, F.; Geerlings, P. Chem.- Eur. J. 2007, 13, 8240
42. Ugur, I.; De Vleeschouwer, F.; Tüzün, N.; Aviyente, V.; Geerlings, P.; Liu, S.; Ayers, P.; De Proft, F. J. Phys. Chem. A 2009, 113, 8704
43. Frisch, M. J. et al. Gaussian 03, Revision B.03; Gaussian, Inc.: Wallingford, CT, 2004.
44. Becke, A. D. J. Chem. Phys. 1993, 98, 5648
45. Lee, C. T.; Yang, W. T.; Parr, R. G. Phys. Rev. B 1988, 37, 785
46. Scott, A. P.; Radom, L. J. Phys. Chem. 1996, 100, 16502
47. Wong, M. W. Chem. Phys. Lett. 1996, 256, 391