A New Specific Mechanism for the Acid Catalysis of the Addition Step in the Baeyer−Villiger Rearrangement

Álvarez-Idaboy, J. Raúl; Reyes, Lino; Cruz, Javier

doi:10.1021/ol060261z

Cited by 91 publications

(102 citation statements)

References 19 publications

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“…These corrections are in good agreement with those independently obtained by Ardura et al [88] and have been successfully used by other authors [89][90][91].…”

Section: Computational Detailssupporting

confidence: 91%

A quantum chemical study on the free radical scavenging activity of tyrosol and hydroxytyrosol

et al. 2012

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The free radical scavenging activity of hydroxytyrosol (HTyr) and tyrosol (Tyr) has been studied in aqueous and lipid solutions, using the density functional theory. Four mechanisms of reaction have been considered: single electron transfer (SET), sequential electron proton transfer (SEPT), hydrogen transfer (HT), and radical adduct formation. It was found that while SET and SEPT do not contribute to the overall reactivity of HTyr and Tyr toward Á OOH and Á OCH 3 radicals, they can be important for their reactions with Á OH, Á OCCl 3 , and Á OOCCl 3 . The Á OOH-scavenging activity of HTyr and Tyr was found to take place exclusively by HT, and it is also predicted to be the main mechanism for their reactions with Á OCH 3 . HT is proposed as the main mechanism for the scavenging activity of HTyr and Tyr when reacting with other Á OR and Á OOR radicals, provided that R is an alkyl or an alkenyl group. The major products of reaction are predicted to be the phenoxyl radicals. In addition, Tyr was found to be less efficient than HTyr as free radical scavenger. Moreover, while HTyr is predicted to be a good peroxyl scavenger, Tyr is predicted to be only moderately for that purpose.

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“…These corrections are in good agreement with those independently obtained by Ardura et al [88] and have been successfully used by other authors [89][90][91].…”

Section: Computational Detailssupporting

confidence: 91%

A quantum chemical study on the free radical scavenging activity of tyrosol and hydroxytyrosol

et al. 2012

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“…This reaction pathway is consistent with the kinetic results and the mechanistic proposal by List and Müller, [46] and it is similar to the mechanism of carboxylic acid catalyzed B-V oxidation using peracids proposed by Alvarez-Idaboy and co-workers. [19,22,23] Rationalization of the reactivities of different ketones towards the B-V reaction: The B-V reactions of acetone, cyclopentanone, and cyclohexanone were also examined theoretically, promoted by 1 c and using hydrogen peroxide as the oxidant. Because both the electrophilicity and hydrogen-bonding capability of these ketones can be expected to be similar to those of cyclobutanone, similar reactivity for the addition was assumed for both cyclic and acyclic ketones.…”

Section: The Phosphoric Acid Bound Criegee Intermediate (Int)mentioning

confidence: 99%

“…The multiple interaction mode for the activation of reactants disclosed in the reaction, that is, the catalyst with two different binding sites in close proximity, seems to be a common feature in several mechanistic models proposed for B-V reactions, and a close resemblance in mechanism can be found between the title reaction and catalysis by carboxylic acids, [19,22,23] metal ions, [25] or zeolites, [26] and thus may represent a promising approach for future catalyst development.…”

mentioning

confidence: 99%

Mechanistic Investigation of Chiral Phosphoric Acid Catalyzed Asymmetric Baeyer–Villiger Reaction of 3‐Substituted Cyclobutanones with H₂O₂ as the Oxidant

Wang

et al. 2010

Chemistry A European J

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The mechanism of the chiral phosphoric acid catalyzed Baeyer-Villiger (B-V) reaction of cyclobutanones with hydrogen peroxide was investigated by using a combination of experimental and theoretical methods. Of the two pathways that have been proposed for the present reaction, the pathway involving a peroxyphosphate intermediate is not viable. The reaction progress kinetic analysis indicates that the reaction is partially inhibited by the gamma-lactone product. Initial rate measurements suggest that the reaction follows Michaelis-Menten-type kinetics consistent with a bifunctional mechanism in which the catalyst is actively involved in both carbonyl addition and the subsequent rearrangement steps through hydrogen-bonding interactions with the reactants or the intermediate. High-level quantum chemical calculations strongly support a two-step concerted mechanism in which the phosphoric acid activates the reactants or the intermediate in a synergistic manner through partial proton transfer. The catalyst simultaneously acts as a general acid, by increasing the electrophilicity of the carbonyl carbon, increases the nucleophilicity of hydrogen peroxide as a Lewis base in the addition step, and facilitates the dissociation of the OH group from the Criegee intermediate in the rearrangement step. The overall reaction is highly exothermic, and the rearrangement of the Criegee intermediate is the rate-determining step. The observed reactivity of this catalytic B-V reaction also results, in part, from the ring strain in cyclobutanones. The sense of chiral induction is rationalized by the analysis of the relative energies of the competing diastereomeric transition states, in which the steric repulsion between the 3-substituent of the cyclobutanone and the 3- and 3'-substituents of the catalyst, as well as the entropy and solvent effects, are found to be critically important.

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“…This is expected since the packing effects of the solvent reduce the entropy loss associated with any addition reaction. This approach has been successfully used before by different authors [37][38][39].…”

Section: Theoretical Study Of the Grafting Of Methyl And 4-nitrobenzymentioning

confidence: 99%

Radical grafting of carbon surfaces with alkylic groups by mediated oxidation of carboxylates

Astudillo

Galano

González

2007

Journal of Electroanalytical Chemistry

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A New Specific Mechanism for the Acid Catalysis of the Addition Step in the Baeyer−Villiger Rearrangement

Cited by 91 publications

References 19 publications

A quantum chemical study on the free radical scavenging activity of tyrosol and hydroxytyrosol

A quantum chemical study on the free radical scavenging activity of tyrosol and hydroxytyrosol

Mechanistic Investigation of Chiral Phosphoric Acid Catalyzed Asymmetric Baeyer–Villiger Reaction of 3‐Substituted Cyclobutanones with H₂O₂ as the Oxidant

Radical grafting of carbon surfaces with alkylic groups by mediated oxidation of carboxylates

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A New Specific Mechanism for the Acid Catalysis of the Addition Step in the Baeyer−Villiger Rearrangement

Cited by 91 publications

References 19 publications

A quantum chemical study on the free radical scavenging activity of tyrosol and hydroxytyrosol

A quantum chemical study on the free radical scavenging activity of tyrosol and hydroxytyrosol

Mechanistic Investigation of Chiral Phosphoric Acid Catalyzed Asymmetric Baeyer–Villiger Reaction of 3‐Substituted Cyclobutanones with H2O2 as the Oxidant

Radical grafting of carbon surfaces with alkylic groups by mediated oxidation of carboxylates

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Mechanistic Investigation of Chiral Phosphoric Acid Catalyzed Asymmetric Baeyer–Villiger Reaction of 3‐Substituted Cyclobutanones with H₂O₂ as the Oxidant