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Volumn 133, Issue 4, 2011, Pages 752-755

Antarafacial mediation of oxygen delivery by a phenylsulfinyl group in the epoxidation of proximal double bonds: Intramolecular trapping of an early Pummerer intermediate with stereoelectronic control

Author keywords

[No Author keywords available]

Indexed keywords

ANTIPERIPLANAR; DOUBLE BONDS; EN-ROUTE; INTRAMOLECULAR TRAPPING; OXYGEN DELIVERY; STEREOSPECIFIC; TRIFLUOROACETATES;

EID: 79851497436     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja1107707     Document Type: Article
Times cited : (11)

References (16)
  • 4
    • 79851502709 scopus 로고    scopus 로고
    • stereochemistry of this epoxide was rigorously proven by crystallographic determination of the structure of the corresponding sulfone
    • The stereochemistry of this epoxide was rigorously proven by crystallographic determination of the structure of the corresponding sulfone.
  • 6
    • 0042377537 scopus 로고    scopus 로고
    • For a general review of activated sulfenium ions as electrophiles, see: a
    • For a general review of activated sulfenium ions as electrophiles, see: (a) Nenaidenko, V. G.; Balenkova, E. S. Russ. T. Org. Chem. 2003, 39, 291-330.
    • (2003) Russ. T. Org. Chem. , vol.39 , pp. 291-330
    • Nenaidenko, V.G.1    Balenkova, E.S.2
  • 7
    • 79851495334 scopus 로고    scopus 로고
    • For an example of a cyclization reaction that is quite different but somewhat related, see
    • For an example of a cyclization reaction that is quite different but somewhat related, see:
  • 9
    • 79851481782 scopus 로고    scopus 로고
    • 8 hydroxyl. Another possibility envisions the potential of participation by the ester-like oxygen in 9 to generate a "high- energy" trifluoroacetylated oxirane, which would cleave instantaneously to provide 4. Finally, one can consider displacement of trifluoroacetate by the resident thionium species to generate the formally dipositive sulfonium, which would be hydrolytically displaced to generate the required β- hydroxysulfonium intermediate en route to the epoxide
    • 8 hydroxyl. Another possibility envisions the potential of participation by the ester-like oxygen in 9 to generate a "high- energy" trifluoroacetylated oxirane, which would cleave instantaneously to provide 4. Finally, one can consider displacement of trifluoroacetate by the resident thionium species to gene]rate the formally dipositive sulfonium, which would be hydrolytically displaced to generate the required β- hydroxysulfonium intermediate en route to the epoxide.
  • 10
    • 0025281231 scopus 로고
    • For a related epoxide formation from an intermediate generated in a totally different fashion, see: a, Indeed, the famous Corey methylenation of carbonyl compounds to generate oxiranes also anticipated, in its last step, a related epoxide formation. See
    • For a related epoxide formation from an intermediate generated in a totally different fashion, see: (a) Corey, E. J.; Su, W. G. Tetrahedron Lett. 1990, 31, 2677-2680. Indeed, the famous Corey methylenation of carbonyl compounds to generate oxiranes also anticipated, in its last step, a related epoxide formation. See:
    • (1990) Tetrahedron. Lett. , vol.31 , pp. 2677-2680
    • Corey, E.J.1    Su, W.G.2
  • 12
    • 79851483205 scopus 로고    scopus 로고
    • Trapping of carbon after deprotonation is a well-known cyclization method associated with the Pummerer reaction. We refer to this process as trapping a late Pummerer intermediate. The intermediates in the present work, where trapping occurs at sulfur, are described as early Pummerer intermediates
    • Trapping of carbon after deprotonation is a well-known cyclization method associated with the Pummerer reaction. We refer to this process as trapping a late Pummerer intermediate. The intermediates in the present work, where trapping occurs at sulfur, are described as early Pummerer intermediates.
  • 14
    • 79851486079 scopus 로고    scopus 로고
    • byproducts obtained in this reaction arise as a mixture of species in which the six-membered ring appears as the homoannular cyclohexadiene or one of the two isomeric conjugated methylenecyclohexenes. The formation of these products is readily accommodated in the mechanistic framework described above
    • The byproducts obtained in this reaction arise as a mixture of species in which the six-membered ring appears as the homoannular cyclohexadiene or one of the two isomeric conjugated methylenecyclohexenes. The formation of these products is readily accommodated in the mechanistic framework described above.
  • 15
    • 0031435223 scopus 로고    scopus 로고
    • For a valuable review of the traditional Pummerer reaction, see
    • For a valuable review of the traditional Pummerer reaction, see: Padwa, A.; Gunn, D. E.; Osterhout, M. H. Synthesis 1997, 1353-1377.
    • (1997) Synthesis , pp. 1353-1377
    • Padwa, A.1    Gunn, D.E.2    Osterhout, M.H.3


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.