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Volumn 64, Issue 2, 1999, Pages 570-580

Six- vs seven-membered ring formation from the 1- bicyclo[4.1.0]heptanylmethyl radical: Synthetic and ab initio studies

Author keywords

[No Author keywords available]

Indexed keywords

1 METHYL 2 METHYLENECYCLOHEXYL RADICAL; 3 METHYLENECYCLOHEPTYL RADICAL; RADICAL; THIOPHENOL; UNCLASSIFIED DRUG;

EID: 0033593265     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo981708n     Document Type: Article
Times cited : (14)

References (75)
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    • (b) Curran, D. P. Radical Cyclizations and Sequential Radical Reactions. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Permagon; Oxford, 1991; Vol. 4, Chapter 4.2, pp 779-831.
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  • 25
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    • 2 is used to generate a ketyl radical adjacent to a cyclopropyl ring, see Batey, R. A.; Motherwell, W. B. Tetrahedron Lett. 1991, 32, 6649-6652.
    • (1991) J. Org. Chem. , vol.56 , pp. 3801-3814
    • Clive, D.L.J.1    Daigneault, S.2
  • 26
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    • 2 is used to generate a ketyl radical adjacent to a cyclopropyl ring, see Batey, R. A.; Motherwell, W. B. Tetrahedron Lett. 1991, 32, 6649-6652.
    • (1972) J. Org. Chem. , vol.37 , pp. 2546-2550
    • Friedrich, E.C.1    Holmstead, R.L.2
  • 27
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    • 2 is used to generate a ketyl radical adjacent to a cyclopropyl ring, see Batey, R. A.; Motherwell, W. B. Tetrahedron Lett. 1991, 32, 6649-6652.
    • (1972) J. Org. Chem. , vol.37 , pp. 2550-2554
    • Friedrich, E.C.1    Holmstead, R.L.2
  • 32
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    • 2 is used to generate a ketyl radical adjacent to a cyclopropyl ring, see Batey, R. A.; Motherwell, W. B. Tetrahedron Lett. 1991, 32, 6649-6652.
    • (1991) J. Org. Chem. , vol.56 , pp. 5285-5289
    • Clive, D.L.J.1    Daigneault, S.2
  • 33
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    • 2 is used to generate a ketyl radical adjacent to a cyclopropyl ring, see Batey, R. A.; Motherwell, W. B. Tetrahedron Lett. 1991, 32, 6649-6652.
    • (1973) J. Org. Chem. , vol.38 , pp. 112-116
    • Thies, R.W.1    McRitchie, D.D.2
  • 34
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    • 2 is used to generate a ketyl radical adjacent to a cyclopropyl ring, see Batey, R. A.; Motherwell, W. B. Tetrahedron Lett. 1991, 32, 6649-6652.
    • (1991) Tetrahedron Lett. , vol.32 , pp. 6649-6652
    • Batey, R.A.1    Motherwell, W.B.2
  • 36
    • 0344071456 scopus 로고    scopus 로고
    • The yield of the ring-expanded product typically is 0-10% in these cases; however, exceptions have been reported: see refs 10a and 13c
    • The yield of the ring-expanded product typically is 0-10% in these cases; however, exceptions have been reported: see refs 10a and 13c.
  • 43
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    • A system similar to 3 has been reported: Dauben, W. G.; Shatter, G. W.; Deviny, E. J. J. Am. Chem. Soc. 1970, 92, 6273-6281. Here, photoexcitation of I led to the ring-expanded 1-acetylcycloheptene (II), but under the conditions of the experiment, the product isolated was primarily the dimerized material. figure presented
    • (1970) J. Am. Chem. Soc. , vol.92 , pp. 6273-6281
    • Dauben, W.G.1    Shatter, G.W.2    Deviny, E.J.3
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    • Also confirmed by TLC analysis
    • Also confirmed by TLC analysis.
  • 51
    • 0000087095 scopus 로고
    • The cyclopropylcarbinyl radical substructure of 3, due to a resonance component which provides additional stabilization, may not react at a rate equal to that of n-butyl radical. For a commentary, see footnote 12 in Newcomb, M.; Glenn, A. G. J. Am. Chem. Soc. 1989, 111, 275-277.
    • (1989) J. Am. Chem. Soc. , vol.111 , pp. 275-277
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  • 60
    • 0345318268 scopus 로고    scopus 로고
    • Although the term σ-bond will generally be used in this discussion in reference to the cyclopropyl skeletal bonds, it is generally acknowledged that these bonds actually incorporate p- as well as s-character
    • Although the term σ-bond will generally be used in this discussion in reference to the cyclopropyl skeletal bonds, it is generally acknowledged that these bonds actually incorporate p- as well as s-character.
  • 61
    • 0345318269 scopus 로고    scopus 로고
    • An alternative view presents itself in the realization that the orbitals which combine to form the cyclopropane σ-bonds have a high degree of p-character, thereby affording good p-p overlap with the radical p-orbital
    • An alternative view presents itself in the realization that the orbitals which combine to form the cyclopropane σ-bonds have a high degree of p-character, thereby affording good p-p overlap with the radical p-orbital.
  • 62
    • 0345318267 scopus 로고    scopus 로고
    • Other factors, assuredly, can modify this ideal situation
    • Other factors, assuredly, can modify this ideal situation.
  • 63
    • 0344455325 scopus 로고    scopus 로고
    • note
    • Though it has been previously suggested for relatively simple systems that build-up of negative charge at the forming radical center in the transition state kinetically favors the primary radical product over the secondary (see ref 2b), our calculations indicate a partial positive charge on the incipient secondary radical center on TS4 which, regardless of steric effects discussed later, should be stabilized by its secondary nature.
  • 64
    • 0344024138 scopus 로고    scopus 로고
    • Biosym Technologies Inc. 9685 Scranton Rd., San Diego, CA 92121-2777
    • InsightII ver 3.2.0 Biosym Technologies Inc. 9685 Scranton Rd., San Diego, CA 92121-2777.
    • InsightII Ver 3.2.0
  • 65
    • 0344024137 scopus 로고    scopus 로고
    • G Wave function Inc. 18401 Von Karman Suite 370, Irvine, CA 92715
    • Spartan SGI version 3.1.2 G Wave function Inc. 18401 Von Karman Suite 370, Irvine, CA 92715
    • Spartan SGI Version 3.1.2
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    • note
    • -1.
  • 69
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    • All zero point energies used in calculating the reported zero point corrected energy values have been subjected to the standard 0.89 frequency scaling factor
    • All zero point energies used in calculating the reported zero point corrected energy values have been subjected to the standard 0.89 frequency scaling factor.
  • 70
    • 0345318266 scopus 로고    scopus 로고
    • 2 hybridized in the product
    • 2 hybridized in the product.
  • 71
    • 0344024134 scopus 로고    scopus 로고
    • note
    • Ab initio calculation results in other cyclopropylcarbinyl radical systems indicate that though these calculations prove quite useful for relative barrier height comparisons, absolute barrier heights should be viewed with some caution (see ref 6a).
  • 73
    • 0344024133 scopus 로고    scopus 로고
    • One should not discount the destabilizing effect on TS6 of the partial adoption of the twist-boat conformation
    • One should not discount the destabilizing effect on TS6 of the partial adoption of the twist-boat conformation.
  • 75
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    • From bond dissociation energies: Benson, S. W. J. Chem. Educ. 1965, 42, 502-518.
    • (1965) J. Chem. Educ. , vol.42 , pp. 502-518
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.