Iodine-mediated Z-selective oxidation of ketones to α,β-unsaturated esters: synthesis and mechanistic studies

The Z-selective oxidation of simple acyclic ketones to Z-2,3-trisubstituted α,β-unsaturated esters is described. Enolates generated under the reaction conditions undergo double iodination followed by a Favorskii-related rearrangement to the unsaturated ester. This reaction represents the first stere...

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Bibliographic Details
Published inTetrahedron letters Vol. 46; no. 48; pp. 8289 - 8292
Main Authors Zacuto, Michael J., Cai, Dongwei
Format Journal Article
LanguageEnglish
Published OXFORD Elsevier Ltd 28.11.2005
Elsevier
Subjects
Acrylates
Chemistry
Chemistry, Organic
Iodine
Oxidation
Physical Sciences
Science & Technology
Acrylates
Oxidation
Iodine
ACID
acrylates
oxidation
STEREOSELECTIVE PREPARATION
iodine
GENERATION
FAVORSKII REARRANGEMENT
FACILE
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Summary:The Z-selective oxidation of simple acyclic ketones to Z-2,3-trisubstituted α,β-unsaturated esters is described. Enolates generated under the reaction conditions undergo double iodination followed by a Favorskii-related rearrangement to the unsaturated ester. This reaction represents the first stereoselective one-step transformation of ketones to α,β-unsaturated esters. Mechanistic studies suggest that an electrocyclic reaction governs the Favorskii-related rearrangement.
ISSN:0040-4039
1873-3581
DOI:10.1016/j.tetlet.2005.09.176