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Volumn 69, Issue 2, 2004, Pages 242-249

Lithium Hexamethyldisilazide-Mediated Ketone Enolization: The Influence of Hindered Dialkyl Ethers and Isostructural Dialkylamines on Reaction Rates and Mechanisms

Author keywords

[No Author keywords available]

Indexed keywords

ACTIVATION ENERGY; AMINES; DIMERS; ETHERS; INFRARED SPECTROSCOPY; LITHIUM COMPOUNDS;

EID: 0346502773     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo030221y     Document Type: Article
Times cited : (19)

References (67)
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    • Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon: New York, Chapter 1
    • (c) Beswick, M. A.; Wright, D. S. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon: New York, 1995; Vol. 1, Chapter 1.
    • (1995) Comprehensive Organometallic Chemistry II , vol.1
    • Beswick, M.A.1    Wright, D.S.2
  • 12
    • 0029870239 scopus 로고    scopus 로고
    • For leading references to structural and mechanistic studies of LiHMDS, see: (a) Lucht, B. L.; Collum, D. B. J. Am. Chem. Soc. 1996, 118, 2217.
    • (1996) J. Am. Chem. Soc. , vol.118 , pp. 2217
    • Lucht, B.L.1    Collum, D.B.2
  • 16
    • 0347821405 scopus 로고    scopus 로고
    • note
    • For evidence that the steric hindrance of amines can make them poor ligands for lithium, see ref 4.
  • 30
    • 84987082416 scopus 로고
    • For leading references and recent examples of detectable organolithium-substrate complexation, see: (a) Klumpp, G. W. Recl. Trav. Chim. Pays-Bas 1986, 105, 1.
    • (1986) Recl. Trav. Chim. Pays-Bas , vol.105 , pp. 1
    • Klumpp, G.W.1
  • 32
    • 0000964801 scopus 로고
    • Trost, B. M., Fleming, I., Eds.; Pergamon: New York
    • For a general discussion of ketone-lithium complexation and related ketone-Lewis acid complexation, see: Shambayati, S.; Schreiber, S. L. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: New York, 1991; Vol. 1, p 283.
    • (1991) Comprehensive Organic Synthesis , vol.1 , pp. 283
    • Shambayati, S.1    Schreiber, S.L.2
  • 39
    • 0345182655 scopus 로고    scopus 로고
    • Isotope effects for LiHMDS-mediated ketone enolizations: (a) Held, G.; Xie, L. F. Microchem. J. 1997, 55, 261.
    • (1997) Microchem. J. , vol.55 , pp. 261
    • Held, G.1    Xie, L.F.2
  • 41
    • 0346561022 scopus 로고    scopus 로고
    • note
    • D = 10-20 as noted in Supporting Information.
  • 42
    • 0346561021 scopus 로고    scopus 로고
    • note
    • 3N mixtures.
  • 43
    • 0347821401 scopus 로고    scopus 로고
    • note
    • The concentration of the lithium amide, although expressed in units of molarity, refers to the concentration of the monomer unit (normality).
  • 45
    • 0345929947 scopus 로고    scopus 로고
    • note
    • For a closely related application of this particular variant of the Job plot, see refs 6b and 8a.
  • 46
  • 47
    • 0020440236 scopus 로고
    • For more recent examples and leading references, see: (b) Huang, C. Y. Methods Enzymol. 1982, 87, 509.
    • (1982) Methods Enzymol. , vol.87 , pp. 509
    • Huang, C.Y.1
  • 50
    • 0347821402 scopus 로고    scopus 로고
    • note
    • 2O] = 1.2 M.
  • 52
    • 0345929946 scopus 로고    scopus 로고
    • note
    • GS The high linearity and simplicity of the relationship is remarkable given that specific through-space (van der Waals) interactions can render steric effects very complex.27


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