Laser flash photolysis studies of alkoxyl radical kinetics using 4-nitrobenzenesulfenate esters as radical precursors

Organic Letters

Volumn 2, Issue 21, 2000, Pages 3369-3372

  Horner, John H ^a   Choi, Seung Yong ^a   Newcomb, Martin ^a  

^a WAYNE STATE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000206311     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol006469g     Document Type: Article

References (45)

1. (a) Paul, H.; Small, R. D., Jr.; Scaiano, J. C. J. Am. Chem. Soc. 1978, 100, 4520-4527.
2. (b) Laarhoven, L. J. J.; Mulder, P. J. Phys. Chem. B 1997, 101, 73-77.
3. (c) Chatgilialoglu, C.; Ingold, K. U.; Lusztyk, J.; Nazran, A. S.; Scaiano, J. C. Organnometallics 1983, 2, 1332-1335.
4. (d) Chatgilialoglu, C.; Scaiano, J. C.; Ingold, K. U. Organnometallics 1982, 1, 466-469.
5. (e) Weber, M.; Fischer, H. J. Am. Chem. Soc. 1999, 121, 7381-7388.
6. (f) Lendvay, G.; Viskolcz, B. J. Phys. Chem. A 1998, 102, 10777-10786.
7. (g) Jungkamp, T. P. W.; Smith, J. N.; Seinfeld, J. H. J. Phys. Chem. A 1997, 101, 4392-4401.
8. (i) Crich, D.; Huang, X.; Newcomb, M. Org. Lett. 1999, 1, 225-227.
9. (j) Petrovic, G.; Cekovic, Z. Tetrahedron Lett. 1997, 38, 627-630.
10. Recent synthetic applications and methods: (a) Hartung, J.; Schwarz, M.; Svoboda, I.; Fuess, H.; Duarte, M. T. Eur. J. Org. Chem. 1999, 1275-1290.
11. (b) Hartung, J.; Kneuer, R. Eur. J. Org. Chem. 2000, 1677-1683.
12. (c) Francisco, C. G.; Martin, C. G.; Suarez, E. J. Org. Chem. 1998, 63, 2099-2109.
13. (d) Guindon, Y.; Denis, R. C. Tetrahedron Lett. 1998, 39, 339-342.
14. (e) Goosen, A.; McCleland, C. W.; Rinaldi, F. C. J. Chem. Soc., Perkin Trans. 2 1993, 279-281.
15. (f) Ellwood, C. W.; Pattenden, G. Tetrahedron Lett. 1991, 32, 1591-1594.
16. (g) Kim, S.; Lee, T. A.; Song, Y. Synlett 1998, 471.
17. (h) Nishida, A.; Nishida, M. Rev. Heteroatom Chem. 1997, 16, 287-311.
18. (i) Saicic, R. N. Tetrahedron Lett. 1997, 38, 295-298.
19. (j) Togo, H.; Muraki, T.; Hoshina, Y.; Yamaguchi, K.; Yokoyama, M. J. Chem. Soc., Perkin Trans. 1 1997, 787-793.
20. (k) Varvoglis, A. Tetrahedron 1997, 53, 1179-1255.
21. (l) Dowd, P.; Zhang, W. Chem. Rev. 1993, 93, 2091-211.
22. (a) Tsentalovich, Y. P.; Kulik, L. V.; Gritsan, N. P.; Yurkovskaya, A. V. J. Phys. Chem. A 1998, 102, 7975-7980.
23. (b) Fittschen, C.; Hippler, H.; Viskolcz, B. Phys. Chem. Chem. Phys. 2000, 2, 1677-1683.
24. (c) Erben-Russ, M.; Michel, C.; Bors, W.; Saran, M. J. Phys. Chem. 1987, 91, 2362-2365.
25. (d) Avila, D. V.; Brown, C. E.; Ingold, K. U.; Lusztyk, J. J. Am. Chem. Soc. 1993, 115, 466-470.
26. (e) Mereau, R.; Rayez, M.-T.; Carlap, F.; Rayez, J.-C. Phys. Chem. Chem. Phys. 2000, 2, 3765-3772.
27. (a) Beckwith, A. L. J.; Hay, B. P. J. Am. Chem. Soc. 1989, 111, 1, 230-234.
28. (b) Nakamura, T.; Busfield, W. K.; Jenkins, I. D. Rizzardo, E.; Thang, S. H.; Suyama, S. J. Org. Chem. 2000, 65, 16-23.
29. (c) Platz, J.; Sehested, J.; Nielsen, O. J.; Wallington, T. J. J. Phys. Chem. A 1999, 103, 2688-2695.
30. (d) Heiss, A.; Sahetchian, K. Int. J. Chem. Kinet. 1996, 28, 531-534.
31. (a) Pasto D. J.; Cottard, F. J. Am. Chem. Soc. 1994, 116, 8973-8977.
32. (b) Pasto, D. J.; Cottard, F.; Picconatto, C. J. Org. Chem. 1994, 59, 7172-7177.
33. Alam, M. M.; Ito, O. J. Org. Chem. 1999, 64, 1285-1290.
34. Wilsey, S.; Dowd, P.; Houk, K. N. J. Org. Chem. 1999, 64, 8801-8811.
35. Walton, J. C. Magn. Reson. Chem. 1987, 25, 998-1000.
36. B3LYP/6-31G** calculations on non-phenylated analogues of 3· and 4· predict that cleavage of the 3-cyclopropyl-2-methyl-2-propoxyl radical to give cyclopropyl-carbinyl radical and acetone should be more exothermic by 1.8 kcal/mol than cleavage of the 3-cyclobutyl-2-methyl-2-propoxyl radical to give the cyclobutylcarbinyl radical and acetone. Recent theoretical work (ref 3e) has shown that B3LYP/6-31G** accurately calculates activation barriers (typically within 2 kcal/mol) for alkoxy radical β-scission.
37. (a) Newcomb, M.; Johnson, C. C.; Manek, M. B.; Varick, T. R. J. Am. Chem. Soc. 1992, 114, 10915-10921.
38. (b) Newcomb, M.; Choi, S. Y.; Homer, J. H. J. Org. Chem. 1999, 64, 1225-1231.
39. (c) Choi, S. Y.; Horner, J. H.; Newcomb, M. J. Org. Chem. 2000, 2, 4447-4449.
40. Heats of formation for the alkoxy radicals were estimated using a bond dissociation energy of 105 kcal/mol for the corresponding alcohol. The heats of formation of the alcohols were estimated by group additivity. In three cases, 12· 13·, and 14·, experimental heats of formation were available for the alcohols (ref 12) and found to match group additivity within 0.2 kcal.
41. Wiberg K. B.; Hao, S. J. Org. Chem. 1991, 56, 5108-5110.
42. (a) Berkowitz, J.; Ellison, G. B.; Gutman, D. J. Phys. Chem. 1994, 98, 2744-2765
43. (b) Marsi, I.; Viskoicz, B. Seres, L. J. Phys. Chem. A 2000, 104, 4497-4504.
44. (c) Seetula, J. A.; Slagle, I. R. J. Chem. Soc., Faraday Trans. 1997, 93, 1709-1719.
45. The data summarized here were obtained in aromatic hydrocarbon solvents (benzene, fluorobenzene, cumene, and (trifluoromethy)lbenzene). The relatively small differences in solvent polarity should have a minimal effect on rates of β-scission.