Efficient catalytic methods for the Baeyer–Villiger oxidation and epoxidation with hydrogen peroxide

Berkessel, Albrecht; Andreae, Marc R. M.

doi:10.1016/s0040-4039(01)00141-1

Cited by 86 publications

(34 citation statements)

References 15 publications

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“…In contrast, we recently reported that in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) as solvent, the Baeyer±Villiger oxidation of 1 to 2 proceeds smoothly and efficiently in the presence of Br˘nsted acid catalysts such as para-toluenesulfonic acid. [10,11] With the aim of developing a generally applicable method for the Baeyer±-Villiger oxidation of nonstrained ketones with hydrogen peroxide, we investigated the mechanism of this remarkably simple process. As it turned out, the formation of 2 from 1 proceeds in a two- A first hint to the formation/decay of a reaction intermediate came from the observation that at temperatures of about 30 8C, ketones such as 1, 2-methylcyclohexanone, or cyclopentanone were consumed rapidly, but the formation of the product lactones lagged behind.…”

mentioning

confidence: 99%

Baeyer–Villiger Oxidations with Hydrogen Peroxide in Fluorinated Alcohols: Lactone Formation by a Nonclassical Mechanism

Berkessel¹,

Andreae²,

Schmickler³

et al. 2002

Angew. Chem. Int. Ed.

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What a difference the solvent makes! Unlike in conventional solvents, nonstrained ketones such as cyclohexanone react smoothly with hydrogen peroxide in 1,1,1,3,3,3‐hexafluoro‐2‐propanol (HFIP) to give lactones. The reaction proceeds via an isolatable spiro‐bisperoxide, which undergoes a highly exothermic acid‐catalyzed rearrangement to two equivalents of lactone (see Equation and IR thermogram).

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confidence: 99%

Baeyer–Villiger Oxidations with Hydrogen Peroxide in Fluorinated Alcohols: Lactone Formation by a Nonclassical Mechanism

Berkessel¹,

Andreae²,

Schmickler³

et al. 2002

Angew. Chem. Int. Ed.

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“…Ethyl esters in esters were formed largely through esterification among active cellulose fragments and ethanol radicals. At the same time, lactones and esters were formed from ketones via Baeyer-Villiger reaction, ring-opening, and redox mechanisms with anhydride as the medium (Berkessel and Andreae 2001;Yamada et al 2007). The pathways of ester formation are shown in Fig.…”

Section: Pathways Of Esters Formationmentioning

confidence: 99%

The Distribution of Bio-Oil Components with the Effects of Sub/Supercritical Ethanol and Free Radicals during Cellulose Liquefaction

Xie

Tang

et al. 2016

BioResources

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Hydroxyl radicals (HO•) and hydrogen radicals (H•) produced from sub/supercritical ethanol have an obvious contribution on cellulose liquefaction for bio-oil production. Salicylic acid was employed as the HO• trap and CCl4 was employed as the H• trap to investigate the role of HO• and H• on the formation pathways of dominant chemical components in bio-oil during cellulose liquefaction in sub/supercritical ethanol (mostly ketones and esters). The yield of bio-oil decreased from 24.7% to 20.7% with the addition of CCl4, while the bio-oil yield increased from 29.3% to 47.9% with the addition of salicylic acid. Gas chromatography/mass spectrometry results showed that the yields of ketones, esters, and phenols in the bio-oil were 22.3%, 8.8%, and 4.7%, respectively, without salicylic acid or CCl4. The highest yields of esters and phenols increased to 21.6% and 36.9%, respectively, in the presence of salicylic acid. The yield of ketones decreased to 14.1%. Experimental data indicated that the cleavage of C-O-C and C-C bonds in the cornstalk cellulose initially generated many active cellulose fragments. Then, platform chemicals were formed from these fragments through aromatization, isomerization, aldol condensation, Baeyer-Villiger oxidation, and trans-Diels-Alder ringopening with the redox of HO• and H•.

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“…4 h, whereas < 10% conversion occurs in the absence of the arsonic acid catalyst [Scheme 1, Equations (2) and (3)]. [8] In solvents such as 1,4-dioxane, no significant conversion of the olefin takes place even in the presence of the arsonic acid catalyst. [8] In view of the remarkably beneficial effect on H 2 O 2 epoxidations, the question arises as to what the mechanistic role of the fluorinated alcohols actually is.…”

Section: Introductionmentioning

confidence: 99%

“…[8] In solvents such as 1,4-dioxane, no significant conversion of the olefin takes place even in the presence of the arsonic acid catalyst. [8] In view of the remarkably beneficial effect on H 2 O 2 epoxidations, the question arises as to what the mechanistic role of the fluorinated alcohols actually is. Based on theoretical studies, Neumann, Shaik et al concluded that the fluoro alcohol provides a charge template, complementary to the H 2 O 2 -alkene moiety, and thereby brings about a specific stabilization of the transition state of olefin epoxidation.…”

Section: Introductionmentioning

confidence: 99%

Kinetic Studies of Olefin Epoxidation with Hydrogen Peroxide in 1,1,1,3,3,3‐Hexafluoro‐2‐propanol Reveal a Crucial Catalytic Role for Solvent Clusters

Berkessel

Adrio

2004

Adv Synth Catal

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The epoxidation of cyclooctene and 1-octene with hydrogen peroxide was studied kinetically in HFIP (1,1,1,3,3,3-hexafluoro-2-propanol)/1,4-dioxane mixtures. In the case of cyclooctene, no additional catalyst was applied, whereas the epoxidation of 1-octene was run in the presence of phenylarsonic acid as catalyst. For both reaction types, two kinetic regimes can be distinguished: at low HFIP concentration (n HFIP /n total X0.15), both the catalyzed and the uncatalyzed reaction show first order dependence on the HFIP concentration. This result is interpreted by the HFIP ™charge template∫ for the uncatalyzed epoxidation (as postulated by Shaik and Neumann) and by the formation of an arsonic acid mono-HFIP ester for the catalyzed reaction. At high HFIP concentration (n HFIP /n total x0.5), both reaction types are up to ca. 5 orders of magnitude faster and show ca. 12 th order dependence on the HFIP concentration. We propose that the dramatic accelerations observed at high HFIP concentrations are brought about by HFIP clusters. Based on literature data (Fioroni, Roccatano, Hong, Suhm), it is concluded that the epoxidation reactions studied here take place in a HFIP coordination sphere comprising ca. 12 HFIP molecules, and that this coordination sphere effects the enormous increases in epoxidation rates. This mechanistic model bears resemblance to enzymatic reactions taking place in and being catalyzed by a protein matrix.

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Efficient catalytic methods for the Baeyer–Villiger oxidation and epoxidation with hydrogen peroxide

Cited by 86 publications

References 15 publications

Baeyer–Villiger Oxidations with Hydrogen Peroxide in Fluorinated Alcohols: Lactone Formation by a Nonclassical Mechanism

Baeyer–Villiger Oxidations with Hydrogen Peroxide in Fluorinated Alcohols: Lactone Formation by a Nonclassical Mechanism

The Distribution of Bio-Oil Components with the Effects of Sub/Supercritical Ethanol and Free Radicals during Cellulose Liquefaction

Kinetic Studies of Olefin Epoxidation with Hydrogen Peroxide in 1,1,1,3,3,3‐Hexafluoro‐2‐propanol Reveal a Crucial Catalytic Role for Solvent Clusters

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