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Volumn 121, Issue 12, 1999, Pages 2863-2874

Reversible interconversion between singlet and triplet 2- naphthyl(carbomethoxy)carbene

Author keywords

[No Author keywords available]

Indexed keywords

2 NAPHTHYL(CARBOMETHOXY)CARBENE; ACETIC ACID DERIVATIVE; CARBONYL DERIVATIVE; CARBOXYLIC ACID DERIVATIVE; KETENE DERIVATIVE; METHYL ALPHA DIAZO(2 NAPHTHYL)ACETATE; NAPHTHYL GROUP; UNCLASSIFIED DRUG;

EID: 0033620447     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja983277w     Document Type: Article
Times cited : (86)

References (120)
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    • Oxirene participation depends on the substrate and reaction conditions. In several instances, isotope labeling experiments exclude the involvement of oxirenes. For examples, see: (a) Majerski, Z.; Redvanly, C. S. J. Chem. Soc., Chem. Commun. 1972, 69. (b) Matlin, S. A.; Sammes, P. G J. Chem. Soc., Perkin Trans. 1 1973, 2851. Timm, U.; Zeller, K.-P.; Meier, H. Tetrahedron 1977, 33, 453.
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    • 3 bond. Experiments (Blom, C. E.; Günthard, Hs. H. Chem. Phys. Lett. 1981, 84, 267) and calculations (Wang, X.; Houk, K. N. J. Am. Chem. Soc. 1988, 110, 1870-1872. Wiberg, K. B.; Laidig, K. E. J. Am. Chem. Soc. 1988, 110, 1872-1874) likewise show that the Z- conformations of esters are more stable than the E-conformations by 5-10 kcal/mol, due to unfavorable dipolar interactions in the latter.
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    • 3 bond. Experiments (Blom, C. E.; Günthard, Hs. H. Chem. Phys. Lett. 1981, 84, 267) and calculations (Wang, X.; Houk, K. N. J. Am. Chem. Soc. 1988, 110, 1870-1872. Wiberg, K. B.; Laidig, K. E. J. Am. Chem. Soc. 1988, 110, 1872-1874) likewise show that the Z-conformations of esters are more stable than the E-conformations by 5-10 kcal/mol, due to unfavorable dipolar interactions in the latter.
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    • note
    • vjb for the other vibrations. Note that, due to the small entropy and heat capacity differences between the different conformers, ΔG will not exhibit a strong temperature dependence.
  • 96
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    • note
    • 2 7839 G.; microwave frequency 9.510 GHz.
  • 100
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    • note
    • 2 transitions were coincident with the corresponding transitions of the major rotamer
  • 102
    • 0344383350 scopus 로고    scopus 로고
    • 25 Since the point spin model is not appropriate to analyze the NCC isomers, the assumption of treating the effects of the substituents on the D values as additive represents an oversimplification
    • 25 Since the point spin model is not appropriate to analyze the NCC isomers, the assumption of treating the effects of the substituents on the D values as additive represents an oversimplification.
  • 103
    • 0344383349 scopus 로고    scopus 로고
    • Note that, by virtue of the substituent priorities in the Cahn-Ingold-Prelog rules, there is a "reversal" in the E/Z-nomeclature in going from MDA to NCC. Thus, (E,E)-MDA yields (Z,Z)-NCC and (E,Z)-MDA gives (Z,E)-NCC (and vice versa)
    • Note that, by virtue of the substituent priorities in the Cahn-Ingold-Prelog rules, there is a "reversal" in the E/Z-nomeclature in going from MDA to NCC. Thus, (E,E)-MDA yields (Z,Z)-NCC and (E,Z)-MDA gives (Z,E)-NCC (and vice versa).
  • 104
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    • 92
    • 92
  • 106
    • 0344383348 scopus 로고    scopus 로고
    • note
    • 78 Our value of ΔE(BCH-BHT) = 3.0 kcal/mol disagrees with the value of 1.4 kcal/mol which can be gathered from Table 2 of ref 78 (both by B3LYP/6-31G* after ZPE correction). The reason is that for BCH (16 in the previous study) the ZPE difference of 0.8 kcal/mol was subtracted instead of added to the energy difference to triplet 2-naphthyl-carbene. The B3LYP/6-31G* entry for 16 should be 3.4 kcal/mol instead of 1.8 kcal/mol.
  • 107
    • 0344815065 scopus 로고    scopus 로고
    • note
    • 72b even B3LYP appears to overestimate the barriers for such reactions.
  • 108
    • 0345677848 scopus 로고    scopus 로고
    • 72b we found ∼48 h at 12 K
    • 72b we found ∼48 h at 12 K.
  • 111
    • 0345677846 scopus 로고    scopus 로고
    • note
    • 105 As this was too expensive to perform for the naphthyl system, we resorted to the corresponding phenyl derivative, which shows a saddle point of very similar structure associated with a similar activation energy relative to the (carbomethoxy)carbene (30.2 kcal/mol). An IRC calculation starting from 1-phenyl-2-methoxyoxirene did indeed show a smooth descent to phenyl(carbomethoxy)carbene in one direction and to benzoyl(methoxy-)carbene in the other direction. We can see no reason this should be different in the naphthyl system.
  • 113
    • 0345677845 scopus 로고    scopus 로고
    • note
    • 0 = -6.0 kcal/mol) takes on a two-step course via a shallow oxirene minimum of much lower relative energy. A more in-depth study of this phenomenon is in progress (Matzinger, S.; Bally, T., to be published).
  • 117
    • 0344383347 scopus 로고    scopus 로고
    • 108,109 Consequently, they lack a thermochemical driving force tor S → T or T → S conversion which could be part of the reason it is not observed
    • 108,109 Consequently, they lack a thermochemical driving force tor S → T or T → S conversion which could be part of the reason it is not observed.
  • 118
    • 0345677843 scopus 로고    scopus 로고
    • note
    • 2 moiety is preserved in the first excited state.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.