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Volumn 46, Issue 42, 2007, Pages 8067-8070

Biomimetic high-valent non-heme iron oxidants for the cis-dihydroxylation and epoxidation of olefins

Author keywords

Dihydroxylation; Epoxidation; Iron; Oxidation; Reaction mechanisms

Indexed keywords

DIHYDROXYLATION; FERRYL COMPLEXES; IRON COMPLEXES; REACTION MECHANISMS;

EID: 35648930973     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200701681     Document Type: Article
Times cited : (132)

References (33)
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    • [7] is not considered to be a biomimetic ferryl complex.
    • [7] is not considered to be a biomimetic ferryl complex.
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    • M. R. Bukowski, P. Comba, A. Lienke, C. Limberg, C. Lopez de Laorden, R. Mas-Ballesté, M. Merz, L. Que. Jr., Angew. Chem. 2006, 118, 3524;
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    • Turnover number TON = 10 x (μmol product per μmol catalyst).
    • Turnover number TON = 10 x (μmol product per μmol catalyst).
  • 21
    • 35648983951 scopus 로고    scopus 로고
    • Formation of, L1)FeV=0(OH, is thermodynamically and kinetically unfavorable with respect to the formation of, L 1)FeIV(OH)2] and, L1)Fe IV=O(OH2, all possible spin states and water-assisted as well as non-water-assisted pathways have been considered, 13] Moreover, the first transition state of the reaction of, L1)Fe V=O(OH, with ethylene has a relative energy of 12 kJ mol -1, which is slightly higher than the corresponding transition state of the, L1)FeIV=O(OH2, based reaction see Supporting Information
    • 2)]-based reaction (see Supporting Information).
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    • This energy barrier has been calculated with Gaussian 03 (G03, there is a small difference to the basis sets used TZVP vs. LACV3P**, which is not expected to have a significant influence on the computed energy barriers
    • This energy barrier has been calculated with Gaussian 03 (G03); there is a small difference to the basis sets used (TZVP vs. LACV3P** + +), which is not expected to have a significant influence on the computed energy barriers.
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    • Preliminary experiments on the dependence of water added to the catalyst solutions lead to significant differences in the total amount of products and product ratios; direct oxidation of the, L1FeII} precursor with tBuOOH or iodosylbenzene diacetate only produces epoxide from cyclooctene. These preliminary experiments support our mechanistic proposal and show how the product selectivity can be tuned
    • II} precursor with tBuOOH or iodosylbenzene diacetate only produces epoxide from cyclooctene. These preliminary experiments support our mechanistic proposal and show how the product selectivity can be tuned.
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.