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Volumn 61, Issue 6, 1996, Pages 2038-2043

A general, highly anti-stereoselective aldolization method via camphor-derived boryl enolates

Author keywords

[No Author keywords available]

Indexed keywords

ALDOL ADDITION; ALDOLIZATION; ALIPHATIC ALDEHYDES; AROMATIC ALDEHYDE; CHIRAL AUXILIARIES; COCATALYST; CONSTRUCTION PROCESS; ENOLATES; HYDROPEROXIDES; NON DESTRUCTIVE; STEREO-SELECTIVE; SYNTHONS;

EID: 0000010580     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9520147     Document Type: Article
Times cited : (39)

References (57)
  • 1
    • 0003417469 scopus 로고
    • For some recent general reviews, see: a, Heathcock, C. H, Ed, Pergamon Press: Oxford, Ch. 1.6
    • For some recent general reviews, see: (a) Heathcock, C. H. In Comprehensive Organic Synthesis; Heathcock, C. H., Ed.; Pergamon Press: Oxford, 1991; Vol. II, Ch. 1.6.
    • (1991) Comprehensive Organic Synthesis , vol.2
    • Heathcock, C.H.1
  • 4
    • 76049123157 scopus 로고    scopus 로고
    • Heathcock, C. H. Asymmetric Synthesis; Morrison, J. D., Ed.; Academic Press: New York, 1984; 3, part B, p 111.
    • (d) Heathcock, C. H. Asymmetric Synthesis; Morrison, J. D., Ed.; Academic Press: New York, 1984; Vol. 3, part B, p 111.
  • 6
    • 0001087242 scopus 로고
    • For related catalytic aldol type reactions, see: a
    • For related catalytic aldol type reactions, see: (a) Mikami, K.; Matsukawa, S. J. Am. Chem. Soc. 1994, 116, 4077.
    • (1994) J. Am. Chem. Soc , vol.116 , pp. 4077
    • Mikami, K.1    Matsukawa, S.2
  • 27
  • 35
    • 0001942351 scopus 로고
    • and references cited therein
    • (c) Heathcock, C. H. Aldrichim. Acta 1990, 23, 99-111, and references cited therein.
    • (1990) Aldrichim. Acta , vol.23 , pp. 99-111
    • Heathcock, C.H.1
  • 45
    • 76049122574 scopus 로고    scopus 로고
    • The rigid 9-BBN moiety had proven to be less sensitive to steric factors than of dialkylboryl in hydroboration reactions, see: Smith, K.; Pelter, A. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, 1991; 8, Chapter 3, p 703.
    • The rigid 9-BBN moiety had proven to be less sensitive to steric factors than of dialkylboryl in hydroboration reactions, see: Smith, K.; Pelter, A. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, 1991; Vol. 8, Chapter 3, p 703.
  • 46
    • 76049099429 scopus 로고    scopus 로고
    • For examples of the reaction stereoselectivity switch by boryl geometry (n-Bu2B-OTf vs 9-BBN-OTf, see: (a) Inoue, T, Uchimaru, T, Mukaiyama, T. Chem. Lett. 1977, 153
    • 2B-OTf vs 9-BBN-OTf), see: (a) Inoue, T.; Uchimaru, T.; Mukaiyama, T. Chem. Lett. 1977, 153.
  • 48
    • 76049120134 scopus 로고    scopus 로고
    • The stereochemical outcome of metal-mediated aldol and related reactions has previously been interpreted employing the open transition state, see: (a) Oare, D, Heathcock, C. H. Topics in Stereochemistry; Eliel, E. L, Wilen, S. H, Eds, John Wiley and Sons: New York, 1991; 20, pp 161-165
    • The stereochemical outcome of metal-mediated aldol and related reactions has previously been interpreted employing the open transition state, see: (a) Oare, D.; Heathcock, C. H. Topics in Stereochemistry; Eliel, E. L., Wilen, S. H., Eds.; John Wiley and Sons: New York, 1991; Vol. 20, pp 161-165.
  • 56
    • 76049092108 scopus 로고    scopus 로고
    • While complete conversion to aldol adducts 7 occurred within 20 min at -90 to -70°C, the corresponding aldol addition of valine-based enolate 2 with Lewis acid-precomplexed aldehyde required 4 h at -78°C. This differential reactivity is important to the high-yield anti-stereoselective aldolization of boryl enolate 6
    • While complete conversion to aldol adducts 7 occurred within 20 min at -90 to -70°C, the corresponding aldol addition of valine-based enolate 2 with Lewis acid-precomplexed aldehyde required 4 h at -78°C. This differential reactivity is important to the high-yield anti-stereoselective aldolization of boryl enolate 6.


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