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Volumn 131, Issue 6, 2009, Pages 2397-2403

Transition-state geometry measurements from13C isotope effects. the experimental transition state for the epoxidation of alkenes with oxaziridines

Author keywords

[No Author keywords available]

Indexed keywords

CHEMISTRY; SYNTHESIS (CHEMICAL);

EID: 67749101413     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja8088636     Document Type: Article
Times cited : (48)

References (63)
  • 23
    • 0034602235 scopus 로고    scopus 로고
    • For an example highlighting a limitation of this process, see
    • For an example highlighting a limitation of this process, see: Singleton, D. A.; Hang, C. J. Org. Chem. 2000, 65, 7554-7560.
    • (2000) J. Org. Chem , vol.65 , pp. 7554-7560
    • Singleton, D.A.1    Hang, C.2
  • 26
    • 23944446462 scopus 로고    scopus 로고
    • Also see ref 12b, which employs a similar process, a Singh, V, Lee, J. E, Nunez, S, Howell, P. L, Schramm, V. L. Biochemistry 2005, 44, 11647-11659
    • Also see ref 12b, which employs a similar process. (a) Singh, V.; Lee, J. E.; Nunez, S.; Howell, P. L.; Schramm, V. L. Biochemistry 2005, 44, 11647-11659.
  • 51
    • 84891744028 scopus 로고    scopus 로고
    • The predicted KIEs for the methyl carbons ranged from 0.998 to 1.000 for 69 different transition structures calculated using B3LYP with various basis sets in the gas phase and with various solvent models.
    • The predicted KIEs for the methyl carbons ranged from 0.998 to 1.000 for 69 different transition structures calculated using B3LYP with various basis sets in the gas phase and with various solvent models.
  • 52
    • 84891737670 scopus 로고    scopus 로고
    • Gaussian, Inc: Wallingford, CT
    • (a) Frisch, M. J.; et al. Gaussian 03, revision C.02; Gaussian, Inc: Wallingford, CT, 2004.
    • (2004) Gaussian 03, revision , Issue.C.02
    • Frisch, M.J.1
  • 53
    • 84891738586 scopus 로고    scopus 로고
    • See the Supporting Information for full details regarding the calculational methods employed
    • (b) See the Supporting Information for full details regarding the calculational methods employed.
  • 57
    • 84891736019 scopus 로고    scopus 로고
    • It should be noted that the Bigeleisen method fully allows for free energy but is less subject to errors in low frequencies than a direct calculation of KIEs from activation free energies see ref 31 and the Supporting Information
    • It should be noted that the Bigeleisen method fully allows for free energy but is less subject to errors in low frequencies than a direct calculation of KIEs from activation free energies (see ref 31 and the Supporting Information).
  • 60
    • 84891747381 scopus 로고    scopus 로고
    • An optimized transition structure of the reaction of ethylene with oxazaridine using a PCM solvent model results in a highly asynchronous structure with bond distances of 1.78 and 2.22 Å and predicted 13C KIEs of 1.023 and 1.010, respectively, which is inconsistent with experimental observations
    • 13C KIEs of 1.023 and 1.010, respectively, which is inconsistent with experimental observations.
  • 61
    • 84891743660 scopus 로고    scopus 로고
    • The set of 70 structures includes all possible transition states explored for the epoxidation of 2-methyl-2-butene catalyzed by 2-(methylsul-fonyl) oxaziridine, trans-3-phenyl-2-methanesulfonyloxaziridine, and cis-3-phenyl-2-methanesulfonyloxaziridine calculated using B3LYP/ 6-31G*, B3LYP/6-31+G**, and B3LYP/6-311+G** in the gas phase, using an implicit Onsager solvent model, or using an implicit PCM solvent model.
    • The set of 70 structures includes all possible transition states explored for the epoxidation of 2-methyl-2-butene catalyzed by 2-(methylsul-fonyl) oxaziridine, trans-3-phenyl-2-methanesulfonyloxaziridine, and cis-3-phenyl-2-methanesulfonyloxaziridine calculated using B3LYP/ 6-31G*, B3LYP/6-31+G**, and B3LYP/6-311+G** in the gas phase, using an implicit Onsager solvent model, or using an implicit PCM solvent model.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.