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Volumn 46, Issue 26, 2007, Pages 4964-4967

CuI-catalyzed conjugate addition of ethyl propiolate

Author keywords

Alkynes; Asymmetric synthesis; Copper; Nucleophilic addition; Synthetic methods

Indexed keywords

ALKYNES; ASYMMETRIC SYNTHESIS; ETHYL PROPIOLATE; NUCLEOPHILIC ADDITION; SYNTHETIC METHODS;

EID: 34447295387     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200701098     Document Type: Article
Times cited : (59)

References (54)
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    • Lee, V.J.1
  • 32
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    • For prior work with lithiated propiolates and C=O addition reactions, see: a M. T. Crimmins, L. E. Guise, Tetrahedron Lett. 1994, 35, 1657-1660;
    • For prior work with lithiated propiolates and C=O addition reactions, see: a) M. T. Crimmins, L. E. Guise, Tetrahedron Lett. 1994, 35, 1657-1660;
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  • 44
    • 3342948302 scopus 로고    scopus 로고
    • β-Aryl-substituted acceptors presented problems for conjugate additions of nitrogen nucleophiles: a C. Palomo, M. Oiarbide, R. Halder, M. Kelso, E. Gomez-Bengoa, J. M. Garcia, J. Am. Chem. Soc. 2004, 126, 9188-9199;
    • β-Aryl-substituted acceptors presented problems for conjugate additions of nitrogen nucleophiles: a) C. Palomo, M. Oiarbide, R. Halder, M. Kelso, E. Gomez-Bengoa, J. M. Garcia, J. Am. Chem. Soc. 2004, 126, 9188-9199;
  • 47
    • 34447337700 scopus 로고    scopus 로고
    • For the reaction using the tert-butyldimethylsilyl(TBS)-protected analogue of 6c, the reaction was very sluggish and the product was isolated as single diastereomer in only 15% yield. The result indicates that the approach of the nucleophile is hindered by the steric bulk of the substrate or the TBS group is preventing the possible coordination of copper propiolate to the γ-oxygen.
    • For the reaction using the tert-butyldimethylsilyl(TBS)-protected analogue of 6c, the reaction was very sluggish and the product was isolated as single diastereomer in only 15% yield. The result indicates that the approach of the nucleophile is hindered by the steric bulk of the substrate or the TBS group is preventing the possible coordination of copper propiolate to the γ-oxygen.
  • 48
    • 34447310250 scopus 로고    scopus 로고
    • See the Supporting Information. CCDC 635258 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/ data_request/cif.
    • See the Supporting Information. CCDC 635258 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/ data_request/cif.
  • 49
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    • For systematic studies on conjugate additions of organocopper reagents to γ-alkoxy-α,β-unsaturated carbonyl compounds, see: a
    • For systematic studies on conjugate additions of organocopper reagents to γ-alkoxy-α,β-unsaturated carbonyl compounds, see: a) Y. Chounan, Y. Ono, S. Nishii, H. Kitahara, S. Ito, Y. Yamamoto, Tetrahedron 2000, 56, 2821-2831;
    • (2000) Tetrahedron , vol.56 , pp. 2821-2831
    • Chounan, Y.1    Ono, Y.2    Nishii, S.3    Kitahara, H.4    Ito, S.5    Yamamoto, Y.6
  • 53
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    • Coordination of the copper propiolate to the γ-oxygen of the acceptor may also be possible. Although the coordinating ability of organocopper reagents is considered insignificant compared to that of organolithium or -magnesium species, there is a striking reactivity difference in this reaction when the γ-oxygen is protected as TBS ether (see Ref. [12]).
    • Coordination of the copper propiolate to the γ-oxygen of the acceptor may also be possible. Although the coordinating ability of organocopper reagents is considered insignificant compared to that of organolithium or -magnesium species, there is a striking reactivity difference in this reaction when the γ-oxygen is protected as TBS ether (see Ref. [12]).
  • 54
    • 32644446865 scopus 로고    scopus 로고
    • I-catalyzed cyclization has been reported: A. Buzas, F. Gagosz, Org. Lett. 2006, 8, 515-518.
    • I-catalyzed cyclization has been reported: A. Buzas, F. Gagosz, Org. Lett. 2006, 8, 515-518.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.