Journal
TETRAHEDRON
Volume 74, Issue 1, Pages 49-57Publisher
PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.tet.2017.11.034
Keywords
Allylic compounds; Manganese; Quinazolinone; Catalysis; Epoxidation; Chemoselectivity; Diastereoselectivity; Reaction mechanisms
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Funding
- Scientific and Technological Research Council of Turkey (TUBITAK) [TBAG-104T399]
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A pair of Mn-III(quinazolinone) complexes was prepared and evaluated in the catalytic epoxidation of the chiral allylic alcohols and unfunctionalised alkenes with iodosylbenzene. Epoxidation of chiral allylic alcohols with 1,3-allylic strain proceeded chemo- and diastereoselectively to give threo-epoxy alcohol (up to 99% d.r). Epoxidation of unfunctionalised alkenes by the proposed catalyst system proceeded nonselectively, as evidenced by the formation of isomerization and rearrangement products in the epoxidation of (Z)-stilbene. A three-step pathway involving a cationic intermediate is proposed for the formation of isomerization and rearrangement products. The fact that only products resulting from the cationic intermediate were detected in the oxidation of a mechanistic probe, (2-methoxy-3-vinylcyclopropyl)benzene, with Mn-III(quinazolinone) and PhIO substantiated the cationic oxygen transfer mechanism. (C) 2017 Elsevier Ltd. All rights reserved.
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