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Volumn 132, Issue 41, 2010, Pages 14617-14624

Through-bond interactions in the diradical intermediates formed in the rearrangements of bicyclo[ n. m.0]alkatetraenes

Author keywords

[No Author keywords available]

Indexed keywords

ALLYLIC RADICALS; B3LYP/6-31G; DIRADICAL INTERMEDIATES; FIVE-MEMBERED RINGS; FOUR-MEMBERED RINGS; SINGLET STATE; SINGLET-TRIPLET; SIX-MEMBERED RINGS; THERMAL REARRANGEMENT; THROUGH-BOND INTERACTIONS; TRANSITION STRUCTURES;

EID: 77958063410     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja106329t     Document Type: Article
Times cited : (10)

References (47)
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    • revision E.01; Gaussian, Inc.: Wallingford, CT,. The full reference is given in the Supporting Information
    • Frisch, M. J.; et al. Gaussian 03, revision E.01; Gaussian, Inc.: Wallingford, CT, 2004. The full reference is given in the Supporting Information.
    • (2004) Gaussian 03
    • Frisch, M.J.1
  • 19
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    • 1 MO the AOs at these two carbons are pure 2p AOs that are tangential to the ring
    • 1 MO the AOs at these two carbons are pure 2p AOs that are tangential to the ring.
  • 21
    • 77958030147 scopus 로고
    • The MOs of cyclobutane have been discussed by
    • The MOs of cyclobutane have been discussed by Salem, L. and Wright, J. S. J. Am. Chem. Soc. 1969, 91, 3947
    • (1969) J. Am. Chem. Soc. , vol.91 , pp. 3947
    • Salem, L.1    Wright, J.S.2
  • 23
  • 24
    • 77958031286 scopus 로고    scopus 로고
    • 1 ring orbital of 2c that is responsible for the 10-12 kcal/mol lower energy of the LUMO of 12b than of 2c
    • 1 ring orbital of 2c that is responsible for the 10-12 kcal/mol lower energy of the LUMO of 12b than of 2c.
  • 25
    • 0001581762 scopus 로고
    • Similar O•- reactions with the appropriate hydrocarbon allowed the generation of the radical anion of tetramethyleneethane
    • Similar O•- reactions with the appropriate hydrocarbon allowed the generation of the radical anion of tetramethyleneethane: Lee, J., Chou, P. K., Dowd, P., and Grabowski, J. J. J. Am. Chem. Soc. 1993, 115, 7902
    • (1993) J. Am. Chem. Soc. , vol.115 , pp. 7902
    • Lee, J.1    Chou, P.K.2    Dowd, P.3    Grabowski, J.J.4
  • 28
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    • For a review and critical discussion of deviations from BEA, see
    • For a review and critical discussion of deviations from BEA, see: Zhang, D. Y. and Borden, W. T. J. Org. Chem. 2002, 67, 3989
    • (2002) J. Org. Chem. , vol.67 , pp. 3989
    • Zhang, D.Y.1    Borden, W.T.2
  • 29
    • 77958050366 scopus 로고    scopus 로고
    • note
    • 3,7]octa-2,6-diene to semibullvalene at 25 °C, (23a, 23b) the very high heat of hydrogenation of the π bond in bicyclo[2.1.1]hex-2-ene, (23c, 23d) and the manner in which annelation by 1,3-bridged cyclobutane rings causes the double bonds in benzene, (23e-23g) cyclooctatetraene, (23h, 23i) and naphthalene (23j) to localize can all be attributed to this type of destabilizing interaction between the filled π orbital of ethylene and a filled orbital of a cyclobutane ring that is 1,3-bridged by a double bond. The long wavelength UV/vis absorptions seen in molecules containing a cyclobutane ring that is 1,3-bridged by ethylene (24a-24d) have been attributed to the same type of interaction between occupied orbitals of the ring and of the unsaturated bridge. (24e-24g)


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