Halogenative Difluorohomologation of Ketones

Fedorov, O.; Kosobokov, Mikhail D.; Levin, Vitalij V.; Стручкова, Марина И.; Dilman, Alexander D.

doi:10.1021/acs.joc.5b00904

Cited by 52 publications

(42 citation statements)

References 53 publications

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“…Either Me 3 SiCF 2 Br or BrF 2 CCO 2 Na may be used as difluorocarbene precursors. In addition, ring opening of the difluorosilacyclopropane intermediate may be induced by an electrophilic source of bromine or iodine yielding 2,2‐difluoro‐3‐haloketones 119 …”

Section: Synthesis Of Difluoroketones By a Fluorinated‐building‐blmentioning

confidence: 99%

Methods for the Synthesis of α,α‐Difluoroketones

Pattison

2018

Eur J Org Chem

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α,α‐Difluoroketones are valuable compounds and can be used as synthetic intermediates for the synthesis of fluorinated molecules, but they also have a direct application in medicinal chemistry, particularly as inhibitors for hydrolytic enzymes. This Microreview will summarize the major methods currently available for the synthesis of α,α‐difluoroketones, highlighting methods involving direct C–F bond formation, as well as those using pre‐difluorinated building blocks.

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Section: Synthesis Of Difluoroketones By a Fluorinated‐building‐blmentioning

confidence: 99%

Methods for the Synthesis of α,α‐Difluoroketones

Pattison

2018

Eur J Org Chem

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“…To improve the procedure, we decided to perform the whole sequence of ketones 1 transformations into the final products without the time‐consuming isolation and purification of enol ethers . For this purpose, the ketones 1 were silylated using a chlorosilane/NaI/NEt 3 combination, and crude silyl enol ethers 2 produced in virtually quantitative yields, were subjected to further reactions with malonyl peroxides 4 without purification (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

“…Preparation of Silyl Enol Ethers 2 [70] NaI (1.4 mmol, 210.0 mg, 1.4 eq.) was placed in a round bottom flask and dried under vacuum (15-20 mmHg) using a heat gun (gun temperature 100-150°C) for 5 min.…”

Section: Experimental Procedures For Schemementioning

confidence: 99%

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

et al. 2019

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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.

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“…Several research groups reported the synthesis of mono fluorinated and difluorinated pyrazoles (Figure ) . In 2014, Sandford and co‐workers pioneered the synthesis of difluorinated pyrazoles under microwave irradiation condition, and obtained a mixture of mono‐ and di‐fluorinated compounds in low yield (Figure a).…”

Section: Introductionmentioning

confidence: 99%