Reactions of tert-butyl peresters. VIII. Preparation of dialkyl tert-butylperoxy phosphates

Sosnovsky, George; Zaret, E. H.

doi:10.1021/jo01256a042

Cited by 25 publications

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“…In fact, comparison of the . [52] Furthermore, different oxidants were employed to assess the enantioselectivity for the catalytic B-V reaction of 3-phenyl cyclobutanone 2 a with 1 b as the catalyst under otherwise identical conditions. The results have shown that the ee values of the lactone 3 a vary significantly with the oxidant employed (Table 1), which is consistent with path B (Scheme 2).…”

Section: Resultsmentioning

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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Section: Resultsmentioning

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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“…Procedures for the preparation of dialkyl phosphorochloridates (1) and sodium ferf-butylperoxide have been previously described 19 . Benzene was dried azeotropically.…”

Section: Methodsmentioning

confidence: 99%

Reactions of tert-Butylperoxy Esters. XV. Decomposition of Dialkyl tert-Butylperoxy Phosphates

Sosnovsky

Zaret

1976

Zeitschrift Für Naturforschung B

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The thermal decomposition of dialkyl £er£-butylperoxy phosphates, in the presence and absence of solvents, yields the corresponding dialkyl phosphate, acetone, methanol, 2,2-dimethoxypropane, and methyl isopropenyl ether as the primary products. Prolonged heating of the product mixture produces trialkyl phosphates, (R0)3P(0), which arise from the thermal decomposition of dialkyl phosphates. Data are presented to support a mechanism involving the heterolytic cleavage of the peroxide linkage.

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“…Peroxyphosphates, for example (EtO) 2 P(O)OO t Bu, (which is shown in Figure ) are more labile than peresters but can often be prepared by relatively similar methods and have been reviewed in detail . Like peresters, they are strong electrophiles; reaction of a Grignard reagent with diethyl tert ‐butyl peroxyphosphate gives a good yield of the tert ‐butyl ether .…”

Section: Related Compoundsmentioning

confidence: 99%

The Chemistry of Peresters

Locklear

Dussault

2020

Eur J Org Chem

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Reactions of tert-butyl peresters. VIII. Preparation of dialkyl tert-butylperoxy phosphates

Cited by 25 publications

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

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

Reactions of tert-Butylperoxy Esters. XV. Decomposition of Dialkyl tert-Butylperoxy Phosphates

The Chemistry of Peresters

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Reactions of tert-butyl peresters. VIII. Preparation of dialkyl tert-butylperoxy phosphates

Cited by 25 publications

References 0 publications

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

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

Reactions of tert-Butylperoxy Esters. XV. Decomposition of Dialkyl tert-Butylperoxy Phosphates

The Chemistry of Peresters

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

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