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Volumn 127, Issue 37, 2005, Pages 12957-12964

Isotope effects on the enzymatic and nonenzymatic reactions of chorismate

Author keywords

[No Author keywords available]

Indexed keywords

BIOSYNTHESIS; ESCHERICHIA COLI; HYDROGEN; POLARIZATION;

EID: 25144441741     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja052929v     Document Type: Article
Times cited : (37)

References (54)
  • 25
    • 25144444646 scopus 로고    scopus 로고
    • note
    • The agreement between theory and experiment is poorer for the heavy atom isotope effects on the elimination reaction than for the Claisen rearrangement, probably due to the indirect nature of the experimental determinations. The discrepancy in the case of the deuterium isotope effects can be attributed to the fact that the one-dimensional tunneling correction is insufficient. An explicit quantum mechanical treatment of the nuclear hydrogen coordinate is likely to be required, but is currently not possible for systems of this size.
  • 43
    • 25144489921 scopus 로고    scopus 로고
    • note
    • This structure has slightly shorter C-O and C-C bond lengths than the transition state reported previously (ret 9), but the effect on the calculated heavy atom isotope effects is small. The relative looseness of the calculated transition state probably reflects electrostatic repulsion of the negatively charged carboxylate groups in the chair geometry, as well as the known bias of the B3LYP method (ref 27).
  • 44
    • 25144469180 scopus 로고    scopus 로고
    • note
    • 13C isotope effect seen at C9 in the enzymatic reactions (Table 1) also argues against a stepwise mechanism, because the bond order to C9 is not expected to decrease substantially in such a process. Although the C-C-O-C torsional mode would be lost in the enolate intermediate, this will not give a full 1% isotope effect.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.