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Volumn 122, Issue 14, 2000, Pages 3288-3295

Isotope effects and the mechanism of chlorotrimethylsilane-mediated addition of cuprates to enones

Author keywords

[No Author keywords available]

Indexed keywords

CARBONYL DERIVATIVE; CYCLOHEXANONE; ISOTOPE; SILANE DERIVATIVE; SOLVENT;

EID: 0034639912     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja993373c     Document Type: Article
Times cited : (74)

References (62)
  • 3
    • 85038130733 scopus 로고
    • Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, Chapter 14
    • (c) Kozlowski, J. A. In Comprehensive Organic Chemistry: Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, 1991; Vol. 4, Chapter 14.
    • (1991) Comprehensive Organic Chemistry , vol.4
    • Kozlowski, J.A.1
  • 21
    • 0001277227 scopus 로고    scopus 로고
    • This proposal has been criticized based on negligible Lewis acidity of TMSC1 itself. See: Lipshutz, B. H.; Aue. D. H.; James, B. Tetrahedron Lett. 1996, 37, 8471. However, this does not exclude the discreet silylation of enones apparently depicted in ref 6.
    • (1996) Tetrahedron Lett. , vol.37 , pp. 8471
    • Lipshutz, B.H.1    Aue, D.H.2    James, B.3
  • 27
    • 84867104302 scopus 로고    scopus 로고
    • Butylcopper is known to add to cyclohexenone at -78°C in the presense of TMSCI. See ref 5b
    • Butylcopper is known to add to cyclohexenone at -78°C in the presense of TMSCI. See ref 5b.
  • 29
    • 33646329806 scopus 로고    scopus 로고
    • note
    • 13C NMR and potential impurities. Small deviations from KIEs of 1.000 for these carbons will not affect the conclusions.
  • 30
    • 33646315924 scopus 로고    scopus 로고
    • This method was developed by S. R. Merrigan in this laboratory
    • This method was developed by S. R. Merrigan in this laboratory.
  • 41
    • 0001615802 scopus 로고
    • Krauss, S. R.; Smith, S. G. J. Am. Chem. Soc. 1981, 103, 141-148. The observed equilibrium in this paper probably reflects a combination of π complex formation and lithium coordination to the enone oxygen.
    • (1981) J. Am. Chem. Soc. , vol.103 , pp. 141-148
    • Krauss, S.R.1    Smith, S.G.2
  • 52
    • 0032943231 scopus 로고    scopus 로고
    • Allowance for the equilibrium presence of the enone π complex as done here may decrease the discrepancy between experimental and calculated isotope effects in these reactions. See: Mori, S.; Nakamura, E. Chem. Eur. 7, 1999, 5, 1534-1543.
    • (1999) Chem. Eur. 7 , vol.5 , pp. 1534-1543
    • Mori, S.1    Nakamura, E.2
  • 55
    • 0029798677 scopus 로고    scopus 로고
    • See especially footnote 20. In addition, a recent paper by one of the original authors in ref 9 also states that with the use of a large excess of TMSCl, hydrolysis of the initially formed silyl enol ether occurs upon workup.
    • Eriksson, M.; Johansson, A.; Nilsson, M.; Olsson, T. J. Am. Chem. Soc. 1996, 118, 10904. See especially footnote 20. In addition, a recent paper by one of the original authors in ref 9 also states that with the use of a large excess of TMSCl, hydrolysis of the initially formed silyl enol ether occurs upon workup.
    • (1996) J. Am. Chem. Soc. , vol.118 , pp. 10904
    • Eriksson, M.1    Johansson, A.2    Nilsson, M.3    Olsson, T.4
  • 59
    • 0002668332 scopus 로고    scopus 로고
    • (a) It is commonly assumed that equilibrium secondary hydrogen isotope effects are an upper bound for the kinetic isotope effect, though exceptions have been noted. See: Glad, S. S.; Jensen, F. J. Org. Chem. 1997, 62, 253.
    • (1997) J. Org. Chem. , vol.62 , pp. 253
    • Glad, S.S.1    Jensen, F.2
  • 60
    • 33646298359 scopus 로고    scopus 로고
    • Modeling of the secondary KIEs using equilibrium isotope effects is bolstered by the expectation that the endothermic silylation step should have a late transition state
    • (b) Modeling of the secondary KIEs using equilibrium isotope effects is bolstered by the expectation that the endothermic silylation step should have a late transition state.
  • 61
    • 33646308858 scopus 로고    scopus 로고
    • Molecular mechanics calculations (MM2) predict that having the tert-butyl group axial in 6-tert-butylcyclohexenone is disfavored by only 0.8 kcal/mol
    • Molecular mechanics calculations (MM2) predict that having the tert-butyl group axial in 6-tert-butylcyclohexenone is disfavored by only 0.8 kcal/mol.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.