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Volumn 73, Issue 7, 2008, Pages 2510-2517

Dramatic effects of halogen substitution and solvent on the rates and mechanisms of nucleophilic substitution reactions of aziridines

Author keywords

[No Author keywords available]

Indexed keywords

COMPUTATION THEORY; MOLECULAR INTERACTIONS; NITROGEN COMPOUNDS; SOLVENTS;

EID: 41649089821     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo7023224     Document Type: Article
Times cited : (12)

References (55)
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    • Ando, W.1    Choi, N.2    Tokitoh, N.3
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    • This reference contains a discussion of the application of NBO atomic charges to aziridines
    • Banks, H. D. J. Org. Chem. 2006, 71, 8089. This reference contains a discussion of the application of NBO atomic charges to aziridines.
    • (2006) J. Org. Chem , vol.71 , pp. 8089
    • Banks, H.D.1
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    • An excellent review of previous syntheses of C-haloaziridines is available: Singh, G. S, D'hooghe, M, De Kimpe, N. Chem. Rev. 2007, 107, 2080
    • An excellent review of previous syntheses of C-haloaziridines is available: Singh, G. S.; D'hooghe, M.; De Kimpe, N. Chem. Rev. 2007, 107, 2080.
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    • The disjoined effect explains the observation of an acceleration of nucleophilic cleavage of three-membered heterocycles in terms of a lowering of the rate-retarding attractive electrostatic energy of the transition state between the partially positively charged carbon reaction center, CR, and the departing partially negative heteroatom functionality. The proposed mechanism of this effect is that advantage is taken of the unpaired electrons of heteroatoms (nitrogen and fluorine) attached to the vicinal carbon, C v. Repulsion of the back lobe of the vicinal carbon orbital used for bonding to the carbon reaction center by these heteroatom electron pairs decreases the magnitude of positive charge assumed by CR relative to a substrate for which this is not possible such as a four-membered ring or an acyclic compound. See Figure 2 and the accompanying text
    • R relative to a substrate for which this is not possible such as a four-membered ring or an acyclic compound. See Figure 2 and the accompanying text.
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    • Excellent reviews of solvent effects are available: (a) Tomasi, J.; Mennucci, B.; Cammi, R. Chem. Rev. 2005, 105, 2999.
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.