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Volumn 121, Issue 41, 1999, Pages 9562-9573

Chiral amino siloxy dienes in the Diels-Alder reaction: Applications to the asymmetric synthesis of 4-substituted and 4,5-disubstituted cyclohexenones and the total synthesis of (-)-α-elemene

Author keywords

[No Author keywords available]

Indexed keywords

ACROLEIN; ALKADIENE; CYCLOHEXANONE; PYRROLIDINE DERIVATIVE;

EID: 0032748432     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9921930     Document Type: Article
Times cited : (75)

References (79)
  • 7
    • 0041524545 scopus 로고
    • Eliel, E. L., Otsuka, S., Eds.; American Chemical Society: Washington, DC
    • (a) Trost, B. M. In Asymmetric Reactions and Processes in Chemistry; Eliel, E. L., Otsuka, S., Eds.; American Chemical Society: Washington, DC, 1982; pp 3-20.
    • (1982) Asymmetric Reactions and Processes in Chemistry , pp. 3-20
    • Trost, B.M.1
  • 8
    • 0042025570 scopus 로고
    • Eliel, E. L., Otsuka, S., Eds.; American Chemical Society: Washington, DC
    • (b) Mukaiyama, T. In Asymmetric Reactions and Processes in Chemistry; Eliel, E. L., Otsuka, S., Eds.; American Chemical Society: Washington, DC, 1982; pp 21-36.
    • (1982) Asymmetric Reactions and Processes in Chemistry , pp. 21-36
    • Mukaiyama, T.1
  • 10
    • 0000123574 scopus 로고    scopus 로고
    • For the chemistry of achiral amino siloxy dienes, see: (a) Kozmin, S. A.; Rawal, V. H. J. Org. Chem. 1997, 62, 5252.
    • (1997) J. Org. Chem. , vol.62 , pp. 5252
    • Kozmin, S.A.1    Rawal, V.H.2
  • 26
    • 0001118395 scopus 로고
    • Morrison, J. D., Ed.; Academic Press: New York
    • (a) Paquette, L. A. In Asymmetric Synthesis; Morrison, J. D., Ed.; Academic Press: New York, 1984; Vol. 3, pp 455-501.
    • (1984) Asymmetric Synthesis , vol.3 , pp. 455-501
    • Paquette, L.A.1
  • 64
    • 0344144857 scopus 로고    scopus 로고
    • note
    • 2-symmetric amines were expected (1d and 1e). Although both dienes were easily prepared using the general procedure outlined in the text (59% and 79% yields, respectively), they did not give superior results in the cycloaddition reactions compared to those obtained with diene 3c, and thus they were not investigated as thoroughly. Diene 3d was prepared from the commercially available secondary amine 1d. It gave a messy reaction with methacrolein and an unpromising 30:24:29:17 mixture of four diastereomers with methyl acrylate. The mannitol-derived compound 1e, was also synthesized and examined briefly. However, diene 3e, derived from this amine, was less reactive than the other dienes, and the yields and ee's were no better than those obtained with diene 3c. The following results were obtained for the cycloaddition/reduction/hydrolysis sequence using diene 3e: (a) methacrolein, 33% yield, 67% ee; (b) methyl acrylate, 63% yield, 75% ee; (c) diethyl fumarate, 57% yield, 85% ee. (matrix presented)
  • 65
    • 0345007290 scopus 로고    scopus 로고
    • note
    • (a) SMP was purchased from Aldrich Chemical Co. (b) RDMP was purchsed from Acros Organics.
  • 70
    • 0344576269 scopus 로고    scopus 로고
    • note
    • The assignment of the relative stereochemistry was made based on the multiplicity of the silyl enol ether proton. In the case of the endo-isomer this proton is observed as a doublet with a J value of 5-6 Hz, due to the coupling to the vicinal proton adjacent to the amino group. The similar resonance corresponding to the exo-diastereomer is usually displayed as a triplet with a very small coupling constant of 1-2 Hz.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.