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Volumn 130, Issue 44, 2008, Pages 14634-14639

Carbene-alkene complexes between a nucleophilic carbene and electron-poor alkenes

Author keywords

[No Author keywords available]

Indexed keywords

HYDROCARBONS; OLEFINS;

EID: 55649100520     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja8042118     Document Type: Article
Times cited : (12)

References (68)
  • 34
    • 55649103523 scopus 로고    scopus 로고
    • Despite many attempts, we could not find the fourth TS syn to syn, probably because of excessive steric hindrance
    • Despite many attempts, we could not find the fourth TS (syn to syn), probably because of excessive steric hindrance.
  • 35
    • 55649107761 scopus 로고    scopus 로고
    • For the purpose of clarity, the usual designations σ, p, π, and π* are used for the description of the orbitals involved in carbene-alkene interactions to present the results of the NBO analysis instead of the notation commonly used by NBO
    • For the purpose of clarity, the usual designations σ, p, π, and π* are used for the description of the orbitals involved in carbene-alkene interactions to present the results of the NBO analysis instead of the notation commonly used by NBO. Therefore, LP corresponds to σ, LP* to p, BD(2) to π, and BD*(2) to π*.
    • Therefore, LP corresponds to σ, LP* to p, BD(2) to π, and BD*(2) to π*
  • 37
    • 33845551316 scopus 로고
    • For the utilization of oxadiazolines in carbene chemistry see, for example:a
    • For the utilization of oxadiazolines in carbene chemistry see, for example:(a) Békhazi, M.; Warkentin, J. J. Am. Chem. Soc. 1983, 105, 1289.
    • (1983) J. Am. Chem. Soc , vol.105 , pp. 1289
    • Békhazi, M.1    Warkentin, J.2
  • 43
    • 55649092508 scopus 로고    scopus 로고
    • In stabilized carbenes, the p-orbital is already partly filled because of intramolecular electron donation. Therefore, during cyclopropanation, electron density can also flow from the p- to the antibonding π-orbital of the alkene. For norbornenylidene, about three-quarters of the interactions arise from donation of the σ-orbital into the π*-orbital; the rest comes from the p-orbital
    • In stabilized carbenes, the p-orbital is already partly filled because of intramolecular electron donation. Therefore, during cyclopropanation, electron density can also flow from the p- to the antibonding π-orbital of the alkene. For norbornenylidene, about three-quarters of the interactions arise from donation of the σ-orbital into the π*-orbital; the rest comes from the p-orbital.
  • 44
    • 55649097813 scopus 로고    scopus 로고
    • As a carbene, norbornenylidene possesses a significant dipole moment (2.44 D, see the Supporting Information). Therefore, the specific geometry found for the complex is due to an additional stabilization resulting from dipole-dipole interactions which favors an antiparallel orientation of the dipole of the carbene and of the alkene (Supporting Information, p S15). The stabilization is also partly due to dipole-induced dipole interactions (Supporting Information, p S16).
    • As a carbene, norbornenylidene possesses a significant dipole moment (2.44 D, see the Supporting Information). Therefore, the specific geometry found for the complex is due to an additional stabilization resulting from dipole-dipole interactions which favors an antiparallel orientation of the dipole of the carbene and of the alkene (Supporting Information, p S15). The stabilization is also partly due to dipole-induced dipole interactions (Supporting Information, p S16).
  • 62
    • 55649090610 scopus 로고    scopus 로고
    • Frisch, M. J.; et al. Gaussian 03; Gaussian, Inc., Pittsburgh, PA, 2003.
    • Frisch, M. J.; et al. Gaussian 03; Gaussian, Inc., Pittsburgh, PA, 2003.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.