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Volumn 125, Issue 45, 2003, Pages 13825-13830

Intramolecular 1,3-Dipolar Ene Reactions of Nitrile Oxides Occur by Stepwise 1,1-Cycloaddition/Retro-Ene Mechanisms

Author keywords

[No Author keywords available]

Indexed keywords

DENSITY FUNCTIONAL THEORY;

EID: 0242407233     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0376487     Document Type: Article
Times cited : (125)

References (39)
  • 1
    • 0000629986 scopus 로고
    • Trost, B. M., Fleming, I., Eds.; Pergamon: Oxford
    • Padwa, A. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: Oxford, 1991; Vol. 4, p 1069.
    • (1991) Comprehensive Organic Synthesis , vol.4 , pp. 1069
    • Padwa, A.1
  • 11
    • 0242561589 scopus 로고    scopus 로고
    • note
    • In the case of amine tether, both the ene-like and the (3+2) products were obtained.5
  • 13
  • 29
    • 0242477773 scopus 로고    scopus 로고
    • note
    • In addition to TS9, there is another approach for the (3+2) path involving addition of C1 to C5 and O to C6. This path can be ruled out according to Bredt's rule.17 No transition state for this path could be located computationally.
  • 31
    • 0000177907 scopus 로고    scopus 로고
    • Another possible path to form the (3+2) product is through the isomerization of 5 to 10. This is similar to the isomerizations of vinylcyclopropanes to cyclopentenes. We could not locate such a transition state, suggesting this path is not possible. For reviews of the isomerizations of vinylcyclopropanes to cyclopentenes, see: (a) Baldwin, J. E. J. Comput. Chem. 1998, 19, 222.
    • (1998) J. Comput. Chem. , vol.19 , pp. 222
    • Baldwin, J.E.1
  • 33
    • 0242394404 scopus 로고    scopus 로고
    • note
    • Computational evidence to support this argument is that the retro-ene reactions shown below have lower activation energies when R is an electron-donating group as compared to the case when R is an electron-withdrawing group. When R is a good π-electron-withdrawing group, such as CHO, the acidity of the (R-)C-H is increased and the corresponding transition state TS27 is only 16.9 kcal/mol higher than 26.
  • 37


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.