Ab Initio MO Calculations for Isomerization Mechanism of the 3-Oxocyclopentylmethyl Radical to the 3-Oxocyclohexyl Radical

Synlett

Volumn 1997, Issue 11, 1997, Pages 1265-1268

  Ryu, Ilhyong ^a   Fukushima, Hiroshi ^a   Okuda, Tohru ^a   Matsu, Kazutoshi ^a   Kambe, Nobuaki ^a   Sonoda, Noboru ^a,b   Komatsu, Mitsuo ^a  

^a OSAKA UNIVERSITY   (Japan)

^b KANSAI UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 2342561941     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-1997-1554     Document Type: Article

References (34)

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11. Carbonylation approach, see: (a) Ryu, I.; Kusano, K.; Hasegawa, M.; Kambe, N.; Sonoda, N. J. Chem. Soc., Chem. Commun. 1991, 1018. (b) Ryu, I.; Yamazaki, H.; Kusano, K.; Ogawa, A.; Sonoda, N. J. Am. Chem. Soc. 1991, 113, 8558. (c) Tsunoi, S.; Ryu, I.; Yamasaki, S.; Fukushima, H.; Tanaka, M.; Komatsu, M.; Sonoda, N. J. Am. Chem. Soc. 1996, 118, 10670. (d) Ryu, I.; Nagahara, K.; Kurihara, A.; Komatsu, M.; Sonoda, N. J. Organomet. Chem. in press. (e) Chatgilialoglu, C.; Ferreri, A.; Sommazzi, A. J. Am. Chem. Soc. 1996, 118, 7223.
12. Carbonylation approach, see: (a) Ryu, I.; Kusano, K.; Hasegawa, M.; Kambe, N.; Sonoda, N. J. Chem. Soc., Chem. Commun. 1991, 1018. (b) Ryu, I.; Yamazaki, H.; Kusano, K.; Ogawa, A.; Sonoda, N. J. Am. Chem. Soc. 1991, 113, 8558. (c) Tsunoi, S.; Ryu, I.; Yamasaki, S.; Fukushima, H.; Tanaka, M.; Komatsu, M.; Sonoda, N. J. Am. Chem. Soc. 1996, 118, 10670. (d) Ryu, I.; Nagahara, K.; Kurihara, A.; Komatsu, M.; Sonoda, N. J. Organomet. Chem. in press. (e) Chatgilialoglu, C.; Ferreri, A.; Sommazzi, A. J. Am. Chem. Soc. 1996, 118, 7223.
13. Carbonylation approach, see: (a) Ryu, I.; Kusano, K.; Hasegawa, M.; Kambe, N.; Sonoda, N. J. Chem. Soc., Chem. Commun. 1991, 1018. (b) Ryu, I.; Yamazaki, H.; Kusano, K.; Ogawa, A.; Sonoda, N. J. Am. Chem. Soc. 1991, 113, 8558. (c) Tsunoi, S.; Ryu, I.; Yamasaki, S.; Fukushima, H.; Tanaka, M.; Komatsu, M.; Sonoda, N. J. Am. Chem. Soc. 1996, 118, 10670. (d) Ryu, I.; Nagahara, K.; Kurihara, A.; Komatsu, M.; Sonoda, N. J. Organomet. Chem. in press. (e) Chatgilialoglu, C.; Ferreri, A.; Sommazzi, A. J. Am. Chem. Soc. 1996, 118, 7223.
14. Carbonylation approach, see: (a) Ryu, I.; Kusano, K.; Hasegawa, M.; Kambe, N.; Sonoda, N. J. Chem. Soc., Chem. Commun. 1991, 1018. (b) Ryu, I.; Yamazaki, H.; Kusano, K.; Ogawa, A.; Sonoda, N. J. Am. Chem. Soc. 1991, 113, 8558. (c) Tsunoi, S.; Ryu, I.; Yamasaki, S.; Fukushima, H.; Tanaka, M.; Komatsu, M.; Sonoda, N. J. Am. Chem. Soc. 1996, 118, 10670. (d) Ryu, I.; Nagahara, K.; Kurihara, A.; Komatsu, M.; Sonoda, N. J. Organomet. Chem. in press. (e) Chatgilialoglu, C.; Ferreri, A.; Sommazzi, A. J. Am. Chem. Soc. 1996, 118, 7223.
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19. 1c Note that even though the mechanism would not be important for the simplest case treated in this study, it would be important for 5-substituted 5-hexenoyl radicals.
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22. For a review see: (a) Dowd, P.; Zhang, W. Chem. Rev. 1993, 93, 2091. See also some examples: (b) Banwell, M. G.; Cameron, J. M. Tetrahedron Lett. 1996, 37, 525. (c) Nemoto, H.; Shiraki, M.; Yamada, N.; Raku, N.; Fukumoto, K. Tetrahedron Lett. 1996, 37, 6355. (d) Boger, D. L.; Mathvink, R. J. J. Org. Chem. 1990, 55, 5442.
23. For a review see: (a) Dowd, P.; Zhang, W. Chem. Rev. 1993, 93, 2091. See also some examples: (b) Banwell, M. G.; Cameron, J. M. Tetrahedron Lett. 1996, 37, 525. (c) Nemoto, H.; Shiraki, M.; Yamada, N.; Raku, N.; Fukumoto, K. Tetrahedron Lett. 1996, 37, 6355. (d) Boger, D. L.; Mathvink, R. J. J. Org. Chem. 1990, 55, 5442.
24. For a review see: (a) Dowd, P.; Zhang, W. Chem. Rev. 1993, 93, 2091. See also some examples: (b) Banwell, M. G.; Cameron, J. M. Tetrahedron Lett. 1996, 37, 525. (c) Nemoto, H.; Shiraki, M.; Yamada, N.; Raku, N.; Fukumoto, K. Tetrahedron Lett. 1996, 37, 6355. (d) Boger, D. L.; Mathvink, R. J. J. Org. Chem. 1990, 55, 5442.
25. For a review see: (a) Dowd, P.; Zhang, W. Chem. Rev. 1993, 93, 2091. See also some examples: (b) Banwell, M. G.; Cameron, J. M. Tetrahedron Lett. 1996, 37, 525. (c) Nemoto, H.; Shiraki, M.; Yamada, N.; Raku, N.; Fukumoto, K. Tetrahedron Lett. 1996, 37, 6355. (d) Boger, D. L.; Mathvink, R. J. J. Org. Chem. 1990, 55, 5442.
26. -1.
27. 8 ΔE from reactant radical to TS-5 chair radical and ΔE from reactant radical to TS-6 chair radical are estimated to be 14.7 and 17.4 kcal/mol at the CASSCF/6-31G* level, respectively. We thank Dr. C. Chatgilialoglu for informing us of this information prior to publication.
28. A part of this work was taken from: Fukushima, H.; M. C. Thesis Osaka University, 1996.
29. Preliminary semiempirical calculations by AM1 and PM3 failed to figure cyclopropoxy radical as a stable structure, as given initial structure of cyclopropoxy radical fell in a ring-opened structure of local minimum.
30. 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.; Gonzales, C.; Martin, R. L.; Fox, D. J.; Defrees, D. J.; Baker, J.; Stewart, J. J. P.; Pople, J. A.: 1992, GAUSSIAN 92, Revision C, Gaussian Inc.: Pittsburgh, PA.
31. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Keith, T.; Petersson, G. A.; Montgomery, J. A.; Raghavachari, K.; Al-Laham, M. A.; Zakrzewski, V. G.; Ortiz, J. V.; Foresman, J. B.; Cioslowski, J.; Stefanov, B. B.; Nanayakkara, A.; Challacombe, M.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; Wong, M. W.; Andres, J. L.; Replogle, E. S.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Binkley, J. S.; Defrees, D. J.; Baker, J.; Stewart, J. P.; Head-Gordon, M.; Gonzalez, C.; Polpe, J. A.: 1995, GAUSSIAN 94, Revision D. 3, Gaussian, Inc.: Pittsburgh, PA.
32. H 21G, C 3-21G, O 3-21G: Binkley, J. S.; Pople, J. A.; Hehre, W. J. J. Am. Chem. Soc. 1980, 102, 939. H 31G: Ditchfield, R.; Hehre, W. J.; Pople, J. A. J. Chem. Phys. 1971, 54, 724 . 6-31G*, O 6-31G*: Hariharan, P. C.; Pople, J. A. Theo. Chim. Acta. 1973, 28, 213.
33. H 21G, C 3-21G, O 3-21G: Binkley, J. S.; Pople, J. A.; Hehre, W. J. J. Am. Chem. Soc. 1980, 102, 939. H 31G: Ditchfield, R.; Hehre, W. J.; Pople, J. A. J. Chem. Phys. 1971, 54, 724 . 6-31G*, O 6-31G*: Hariharan, P. C.; Pople, J. A. Theo. Chim. Acta. 1973, 28, 213.
34. H 21G, C 3-21G, O 3-21G: Binkley, J. S.; Pople, J. A.; Hehre, W. J. J. Am. Chem. Soc. 1980, 102, 939. H 31G: Ditchfield, R.; Hehre, W. J.; Pople, J. A. J. Chem. Phys. 1971, 54, 724 . 6-31G*, O 6-31G*: Hariharan, P. C.; Pople, J. A. Theo. Chim. Acta. 1973, 28, 213.