Radical intermediates in the Jacobsen-Katsuki epoxidation

Angewandte Chemie - International Edition

Volumn 39, Issue 3, 2000, Pages 589-592

  Cavallo, Luigi ^b   Jacobsen, Heiko ^a  

^a UNIVERSITY OF ZURICH   (Switzerland)

^b UNIVERSITY OF NAPLES FEDERICO II   (Italy)

Author keywords

Asymmetric synthesis; Density functional calculations; Epoxidations; Oxidations; Radicals

Indexed keywords

ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; EPOXIDATION; GEOMETRY; ISOMERISM; OPTICAL ROTATION; REACTION ANALYSIS;

EID: 0034603013     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3773(20000204)39:3<589::AID-ANIE589>3.0.CO;2-0     Document Type: Article

References (30)

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18. [12] Main group elements were described by a double ζ STO basis including one polarization function, whereas for Mn a triple ζ STO basis with one additional 4p function was used (ADF basis sets III and IV, respectively). Transition states have been characterized by one negative eigenvalue of the approximate Hessian, and by a coordinate-tracing procedure. For more computational details and further references, see ref. [12d].
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24. 1 are needed to give rise to stable ethene-coordinated species. A similar - TΔS contribution to the free energy of epoxide coordination, and hence similar conclusions, can also be reasonably assumed in the present study.
25. 1 are needed to give rise to stable ethene-coordinated species. A similar - TΔS contribution to the free energy of epoxide coordination, and hence similar conclusions, can also be reasonably assumed in the present study.
26. 1 are needed to give rise to stable ethene-coordinated species. A similar - TΔS contribution to the free energy of epoxide coordination, and hence similar conclusions, can also be reasonably assumed in the present study.
27. C. Linde, B. Åkermark, P.-O. Norrby, M. Svensson, J. Am. Chem. Soc. 1999, 121, 5083.
28. Consult the supporting information for optimized geometries and final energies of all species.
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30. V-oxo complexes, see also ref. [15]. For 2 and 10, no complexes possessing S0-ground states could be localized.