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Volumn 54, Issue 40, 1998, Pages 12161-12172

1,2-Hydrogen shifts in thermal and photic Bamford-Stevens reactions of cyclohexanones. Activation by an endocyclic oxygen

Author keywords

[No Author keywords available]

Indexed keywords

CYCLOHEXANONE DERIVATIVE; OXYGEN;

EID: 0032191723     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4020(98)00757-1     Document Type: Article
Times cited : (11)

References (50)
  • 1
    • 0002958913 scopus 로고
    • 1. Bamford, W.R.; Stevens, T.S. J. Chem. Soc. C 1952, 4735-4740. For reviews of the Bamford-Stevens reaction see: (a) Kirmse, W. Carbene Chemistry, 2nd ed.; Academic: New York, 1971.
    • (1952) J. Chem. Soc. C , pp. 4735-4740
    • Bamford, W.R.1    Stevens, T.S.2
  • 2
    • 0004050551 scopus 로고
    • Academic: New York
    • 1. Bamford, W.R.; Stevens, T.S. J. Chem. Soc. C 1952, 4735-4740. For reviews of the Bamford-Stevens reaction see: (a) Kirmse, W. Carbene Chemistry, 2nd ed.; Academic: New York, 1971.
    • (1971) Carbene Chemistry, 2nd Ed.
    • Kirmse, W.1
  • 6
    • 0002216732 scopus 로고
    • 3. For a discussion and leading references see: Nickon, A. Acc. Chem. Res. 1993, 26, 84-89.
    • (1993) Acc. Chem. Res. , vol.26 , pp. 84-89
    • Nickon, A.1
  • 8
    • 0001062264 scopus 로고
    • 5. Theoretical calculations suggest that at the transition state, even though the migrating H has not moved far along the reaction coordinate ("early" transition state), the nonmigrating groups are positioned similarly as in the alkene product (a) Evanseck, J.D.; Houk, K.N. J. Am. Chem. Soc. 1990, 112, 9148-9156.
    • (1990) J. Am. Chem. Soc. , vol.112 , pp. 9148-9156
    • Evanseck, J.D.1    Houk, K.N.2
  • 12
    • 85038554360 scopus 로고    scopus 로고
    • Published product ratio data upon which all migration ratios are based do not warrant use of three significant figures, especially when one product component is formed in small proportion relative to another component (see for e.g., Table 1 in reference 3). However, we retain three figures for discussion so readers can readily connect them to numbers that have appeared in several earlier publications. Any final conclusions should take into account the quantitative limitations of the data
    • (b) Published product ratio data upon which all migration ratios are based do not warrant use of three significant figures, especially when one product component is formed in small proportion relative to another component (see for e.g., Table 1 in reference 3). However, we retain three figures for discussion so readers can readily connect them to numbers that have appeared in several earlier publications. Any final conclusions should take into account the quantitative limitations of the data.
  • 14
    • 0027197861 scopus 로고
    • (b) Stern, A.G.; Ilao, M.C.; Nickon, A. Tetrahedron 1993, 49, 8107-8118. The reported photochemical value (1.17 at 25 °C) becomes 1.40 after adjustment for isotope effects as described in ref. 6a, footnote 32.
    • (1993) Tetrahedron , vol.49 , pp. 8107-8118
    • Stern, A.G.1    Ilao, M.C.2    Nickon, A.3
  • 16
    • 85038544631 scopus 로고    scopus 로고
    • Note that in the transition state for shift of the 3° H in each epimer of 2, the bystander OMe must necessarily be anti to the ring methylene at C-6
    • 9. Note that in the transition state for shift of the 3° H in each epimer of 2, the bystander OMe must necessarily be anti to the ring methylene at C-6.
  • 19
    • 0002289447 scopus 로고
    • and references cited there
    • 12. Unlike B-S reactions, in which it is important to use just one equivalent of strong base (e.g. RLi), Shapiro reactions utilize excess base and involve different intermediates. Chamberlin, R.A.; Bloom, S.H. Org. Reactins 1990, 39, 1-83 and references cited there.
    • (1990) Org. Reactins , vol.39 , pp. 1-83
    • Chamberlin, R.A.1    Bloom, S.H.2
  • 24
    • 85038552359 scopus 로고    scopus 로고
    • Personal communication
    • 16. Shechter, H. Personal communication. See: Gould, K.A. Ph.D. Thesis, The Ohio State University, 1975; Diss. Absir. Int. 1975, 36, 2806-B.
    • Shechter, H.1
  • 25
    • 85038548326 scopus 로고
    • Ph.D. Thesis, The Ohio State University
    • 16. Shechter, H. Personal communication. See: Gould, K.A. Ph.D. Thesis, The Ohio State University, 1975; Diss. Absir. Int. 1975, 36, 2806-B.
    • (1975)
    • Gould, K.A.1
  • 26
    • 85038550207 scopus 로고
    • 16. Shechter, H. Personal communication. See: Gould, K.A. Ph.D. Thesis, The Ohio State University, 1975; Diss. Absir. Int. 1975, 36, 2806-B.
    • (1975) Diss. Absir. Int. , vol.36
  • 29
    • 0002312550 scopus 로고
    • Brinker, U.H., Ed.; JAI Press, Greenwich, CT
    • (c) Jackson, J.E.; Platz, M.S. in Advances in Carbene Chemistry, Brinker, U.H., Ed.; JAI Press, Greenwich, CT, Vol 1, 1994, pp 89-160.
    • (1994) Advances in Carbene Chemistry , vol.1 , pp. 89-160
    • Jackson, J.E.1    Platz, M.S.2
  • 48
    • 85038540375 scopus 로고
    • Ph.D. Dissertation, Johns Hopkins University
    • 27. For additional details see Kim, K. Ph.D. Dissertation, Johns Hopkins University, 1986.
    • (1986)
    • Kim, K.1
  • 49
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    • Carbon analysis on this sample was ca. 4% low and after one sublimation was ca. 1% low, presumably from tenacious residual solvent(s) of recrystallization. Possible contamination by enol ether 7 (or its hemiacetal precursor) or by epimer 8a would not account for low carbon analyses
    • 28. Carbon analysis on this sample was ca. 4% low and after one sublimation was ca. 1% low, presumably from tenacious residual solvent(s) of recrystallization. Possible contamination by enol ether 7 (or its hemiacetal precursor) or by epimer 8a would not account for low carbon analyses.


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