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Volumn 73, Issue 8, 2008, Pages 2980-2994

Role of negative hyperconjugation and anomeric effects in the stabilization of the intermediate in SNV reactions

Author keywords

[No Author keywords available]

Indexed keywords

CONFORMATIONS; DENSITY FUNCTIONAL THEORY; IONS; THERMODYNAMIC STABILITY;

EID: 84961980514     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo7017476     Document Type: Article
Times cited : (20)

References (88)
  • 1
    • 25844473874 scopus 로고
    • NV mechanism: (a) Rappoport, Z
    • NV mechanism: (a) Rappoport, Z. Adv. Phys. Org. Chem. 1969, 7, 1.
    • (1969) Adv. Phys. Org. Chem , vol.7 , pp. 1
  • 5
    • 84962403935 scopus 로고
    • 1992, 25, 474.
    • (1992) , vol.474 , Issue.25
  • 9
    • 84962383746 scopus 로고    scopus 로고
    • In contrast to the LG being an alkyl group, phenyl group, or hydrogen
    • In contrast to the LG being an alkyl group, phenyl group, or hydrogen.
  • 22
    • 84962403816 scopus 로고    scopus 로고
    • The intrinsic barrier of a reaction refers to the barrier in the absence of a thermodynamic driving force.8b
    • 8b
  • 38
    • 0032746607 scopus 로고    scopus 로고
    • Yokoyama, Y.; Ohashi, Y. Bull. Chem. Soc. Jpn. 1999, 72, 2183. See also references cited in the papers above.
    • (j) Yokoyama, Y.; Ohashi, Y. Bull. Chem. Soc. Jpn. 1999, 72, 2183. See also references cited in the papers above.
  • 43
    • 84962417566 scopus 로고    scopus 로고
    • Equation 2 includes only the 2-fold component of a more general equation suggested in ref 10b
    • (b) Equation 2 includes only the 2-fold component of a more general equation suggested in ref 10b.
  • 44
    • 84962417569 scopus 로고    scopus 로고
    • -).
    • -).
  • 47
    • 84962445215 scopus 로고    scopus 로고
    • Gaussian 98 (revision A.11) and Gaussian 03 (revision B.05): M. J. Frisch, et al., Gaussian, Inc., Pittsburgh, PA, 2001. The complete reference is given in the Supporting Information.
    • Gaussian 98 (revision A.11) and Gaussian 03 (revision B.05): M. J. Frisch, et al., Gaussian, Inc., Pittsburgh, PA, 2001. The complete reference is given in the Supporting Information.
  • 56
    • 84962355903 scopus 로고    scopus 로고
    • NBO, v 5.0: Glendening, E. D.; Badenhoop, J. K.; Reed, A. E.; Carpenter, J. E.; Bohmann, J. A.; Morales, C. M.; Weinhold, F., Theoretical Chemistry Institute, University of Wisconsin, Madison, WI, 2001; http://www.chem.wisc.edu/_nbo5.
    • (a) NBO, v 5.0: Glendening, E. D.; Badenhoop, J. K.; Reed, A. E.; Carpenter, J. E.; Bohmann, J. A.; Morales, C. M.; Weinhold, F., Theoretical Chemistry Institute, University of Wisconsin, Madison, WI, 2001; http://www.chem.wisc.edu/_nbo5.
  • 61
    • 84962358732 scopus 로고    scopus 로고
    • To test the reliability of this method for calculating pK a values and stabilization trends in our systems, we calculated pKa differences (ΔpKa) in water solution between HA and HB according to HA, B- → HB, A, ΔpKa, ΔGgas, ΔGsolv)/2.3RT (T, 298 K).21b ΔpKa(CF3CH2OH-CH3OH, 5.3 (experimental -3.1),21c,d ΔpKa(Meldrum acid (19b, CF3CH2OH, 6.2 (experimental -7.6),21c,d and ΔpKa(Meldrum acid (19b, CH3OH, 11.6 (experimental -10.7).21c,d Part of the computational error results from errors in the computated ΔGgas. However, the trends are well reproduced. 21e
    • 21e
  • 67
    • 84962417519 scopus 로고    scopus 로고
    • α = -69.3° and -65.9°.
    • α = -69.3° and -65.9°.
  • 68
    • 84962417520 scopus 로고    scopus 로고
    • β bonds of 1.105 and 1.426 Å, respectively.
    • β bonds of 1.105 and 1.426 Å, respectively.
  • 70
    • 84962407236 scopus 로고    scopus 로고
    • The p(X) → σ*(Cβ-X) NBO energy differences are (eV) 12.1 (2p(CH3O) → σ*(C β-SCH3, < 14.5 (3p(CH3S) → σ*(Cβ-OCH3, 15.8 (2p(OCH3) → σ*(Cβ-OCH2CF3, < 16.9 (2p(CF3CH2O) → σ*(C β-OCH3, and 12.9 (2p(OCH2CF3) → σ*(Cβ-SCH3, < 14.2 (3p(SCH3) → σ*Cβ-OCH 2CF3
    • 3)).
  • 71
    • 84962387903 scopus 로고    scopus 로고
    • A significantly smaller stabilizing effect is caused by the interaction between the lone pairs on O and S and the σ*C-CH2 , orbital. Its contribution to the stability of 7b and 7c is calculated to be ca. 2.0 kcal/mol
    • -) orbital. Its contribution to the stability of 7b and 7c is calculated to be ca. 2.0 kcal/mol.
  • 72
    • 84962387900 scopus 로고    scopus 로고
    • 21b,c
    • 21b,c
  • 75
    • 84962417551 scopus 로고    scopus 로고
    • In all reactions where the substituents are being separated from each other, we have to consider the release of steric repulsion between the geminal X and Z substituents
    • (a) In all reactions where the substituents are being separated from each other, we have to consider the release of steric repulsion between the geminal X and Z substituents.
  • 76
    • 84962417557 scopus 로고    scopus 로고
    • 7a,d
    • 7a,d
  • 87
    • 84962381925 scopus 로고    scopus 로고
    • 31
    • 31


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.