Hypervalent Iodine Oxidants: Structure and Kinetics of the Reactive Intermediates in the Oxidation of Alcohols and 1,2-Diols by o-Iodoxybenzoic Acid (IBX) and Dess−Martin Periodinane. A Comparative 1H-NMR Study
Alcohols and 1,2-diols oxidation by o-iodoxybenzoic acid (IBX) has been examined by 1H-NMR spectroscopy. Reversible formation of reactive intermediates, iodic esters 5, has been observed, and their structures in DMSO-d 6 solution have been defined as 10-I-4 axial alkoxyiodinane oxides by comparison...
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Published in | Journal of organic chemistry Vol. 61; no. 26; pp. 9272 - 9279 |
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Main Authors | , , |
Format | Journal Article |
Language | English |
Published |
American Chemical Society
27.12.1996
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Abstract | Alcohols and 1,2-diols oxidation by o-iodoxybenzoic acid (IBX) has been examined by 1H-NMR spectroscopy. Reversible formation of reactive intermediates, iodic esters 5, has been observed, and their structures in DMSO-d 6 solution have been defined as 10-I-4 axial alkoxyiodinane oxides by comparison of the chemical shift difference data with those obtained for Dess−Martin periodinane (DMP)−alcoholate and −diolate adducts. The dichotomous behavior exhibited by IBX and DMP with 1,2-diols can be explained in terms of the different architecture of the reactive intermediates involved in the oxidation. With aliphatic alcohols, kinetic evidences support a two-step reaction mechanism involving a fast pre-equilibrium step leading to 5, followed by a rate-determining disproportionation step. With electronically activated benzyl alcohol, the attainment of pre-equilibrium is largely dependent on initial water concentration as a consequence of a particularly high k 2 value. The influence of the alcohol structure on measured equilibrium (K eq) and rate constants (k 2) and the effect of water on the overall reaction rate are discussed. |
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AbstractList | Alcohols and 1,2-diols oxidation by o-iodoxybenzoic acid (IBX) has been examined by 1H-NMR spectroscopy. Reversible formation of reactive intermediates, iodic esters 5, has been observed, and their structures in DMSO-d 6 solution have been defined as 10-I-4 axial alkoxyiodinane oxides by comparison of the chemical shift difference data with those obtained for Dess−Martin periodinane (DMP)−alcoholate and −diolate adducts. The dichotomous behavior exhibited by IBX and DMP with 1,2-diols can be explained in terms of the different architecture of the reactive intermediates involved in the oxidation. With aliphatic alcohols, kinetic evidences support a two-step reaction mechanism involving a fast pre-equilibrium step leading to 5, followed by a rate-determining disproportionation step. With electronically activated benzyl alcohol, the attainment of pre-equilibrium is largely dependent on initial water concentration as a consequence of a particularly high k 2 value. The influence of the alcohol structure on measured equilibrium (K eq) and rate constants (k 2) and the effect of water on the overall reaction rate are discussed. |
Author | Frigerio, Marco De Munari, Sergio Santagostino, Marco |
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Copyright | Copyright © 1996 American Chemical Society |
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Snippet | Alcohols and 1,2-diols oxidation by o-iodoxybenzoic acid (IBX) has been examined by 1H-NMR spectroscopy. Reversible formation of reactive intermediates, iodic... |
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Title | Hypervalent Iodine Oxidants: Structure and Kinetics of the Reactive Intermediates in the Oxidation of Alcohols and 1,2-Diols by o-Iodoxybenzoic Acid (IBX) and Dess−Martin Periodinane. A Comparative 1H-NMR Study |
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