Alkene Dihydroxylation with Malonoyl Peroxides: Catalysis Using Fluorinated Alcohols

Picon, Sylvain; Rawling, Michael J.; Campbell, Matthew; Tomkinson, Nicholas C. O.

doi:10.1021/ol3030154

Cited by 48 publications

(17 citation statements)

References 31 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This mechanistic pathway is consistent with previous investigations of the reactivity of the malonyl peroxides 4 . Based on the obtained results we can consider the discovered oxidative C−O coupling of malonyl peroxides with enol ethers as oxidative [5+2] cycloaddition from the formal point of view.…”

Section: Resultssupporting

confidence: 92%

C−O coupling of Malonyl Peroxides with Enol Ethers via [5+2] Cycloaddition: Non‐Rubottom Oxidation

et al. 2019

View full text Add to dashboard Cite

Malonyl peroxides act both as oxidants and reagents for C−O coupling in reactions with methyl and silyl enol ethers. In the proposed conditions, the oxidative C−O coupling of malonyl peroxides with enol ethers selectively proceeds, bypassing the traditional Rubottom hydroxylation of enol ethers by peroxides. It was observed that the oxidative [5+2] cycloaddition of malonyl peroxides and enol ethers is the key stage of the discovered process. Oxidative C−O coupling of silyl enol ethers leads to the formation of α‐acyloxyketones with a free carboxylic acid group. A specially developed preparative one‐pot procedure transforms ketones via silyl enol ethers formation and the following coupling into α‐acyloxyketones with yields 35–88%. The acid‐catalyzed coupling with methyl enol ethers gives remarkable products while retaining the easily oxidizable enol fragment. Furthermore, these molecules contain a free carboxylic acid group, thus these nontrivial products contain two usually incompatible acid and enol ether groups.

show abstract

Section: Resultssupporting

confidence: 92%

C−O coupling of Malonyl Peroxides with Enol Ethers via [5+2] Cycloaddition: Non‐Rubottom Oxidation

et al. 2019

View full text Add to dashboard Cite

show abstract

“…FTIR (KBr): 3472, 2923, 1941, 1628, 1364 cm –1 . Analytical data are in accordance with literature data …”

Section: Experimental Sectionsupporting

confidence: 85%

A General Method for Photocatalytic Decarboxylative Hydroxylation of Carboxylic Acids

Khan

Zaman

et al. 2020

J. Org. Chem.

View full text Add to dashboard Cite

A general and practical method for decarboxylative hydroxylation of carboxylic acids was developed through visible light-induced photocatalysis using molecular oxygen as the green oxidant. The addition of NaBH4 to in situ reduce the unstable peroxyl radical intermediate much broadened the substrate scope. Different sp3 carbon-bearing carboxylic acids were successfully employed as substrates, including phenylacetic acid-type substrates, as well as aliphatic carboxylic acids. This transformation worked smoothly on primary, secondary, and tertiary carboxylic acids.

show abstract

“…Interestingly, it has been shown that fluorinated alcohols can be used to accelerate reactions involving peroxides. 50,51 It has also been shown that fluorinated alcohols have the ability to activate hydrogen peroxide, 52 which has been specifically exploited in oxidation reactions. Examination of hexafluoroisopropanol (HFIP) as an alternative reaction solvent resulted in an equivalent conversion of cyclohexanone 4 to the ester 5 (42%; entry 12).…”

Section: Optimization Of the Baeyer-villiger Reactionmentioning

confidence: 99%

Baeyer–Villiger oxidation under Payne epoxidation conditions

2015

View full text Add to dashboard Cite

A novel method for the Baeyer–Villiger oxidation of ketones has been developed and optimized. The transformation involves a transition metal-free activation of hydrogen peroxide under Payne epoxidation conditions. Reaction of a ketone with hydrogen peroxide in the presence of a nitrile under mildly basic reaction conditions leads to the corresponding ester. The transformation has been successfully applied to a range of ketones in moderate to excellent yields (30–91 and good to excellent regioselectivities (7:1 to 20:1)

show abstract

Alkene Dihydroxylation with Malonoyl Peroxides: Catalysis Using Fluorinated Alcohols

Cited by 48 publications

References 31 publications

C−O coupling of Malonyl Peroxides with Enol Ethers via [5+2] Cycloaddition: Non‐Rubottom Oxidation

C−O coupling of Malonyl Peroxides with Enol Ethers via [5+2] Cycloaddition: Non‐Rubottom Oxidation

A General Method for Photocatalytic Decarboxylative Hydroxylation of Carboxylic Acids

Baeyer–Villiger oxidation under Payne epoxidation conditions

Contact Info

Product

Resources

About