Preparation of (Phenyldifluoromethyl)- and (Phenoxydifluoromethyl)-silanes by Magnesium-Promoted Carbon-Chlorine Bond Activation

Controlling the cleavage of carbon−carbon bonds during a chemical reaction is a substantial challenge; however, synthetic methods that accomplish this objective produce valuable and often unexplored reactivity. We have designed a mild process to generate α,α-difluorobenzyl carbanions in the presence of potassium carbonate by exploiting the cleavage of C−C bonds during the release of trifluoroacetate. The initiating reagent is potassium carbonate, which represents an improvement over existing protocols that require a strong base. Fragmentation studies across substituted arenes and heteroarenes were conducted along with computational analyses to elucidate reactivity trends. Furthermore, the mildly generated α,α-difluorobenzyl carbanions from electron-deficient aromatics and heteroaromatic rings can react with aldehydes to create derivatives of difluoromethylbenzenes, which are valuable synthetic targets.

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Controlling the Cleavage of Carbon–Carbon Bonds To Generate α,α-Difluorobenzyl Carbanions for the Construction of Difluoromethylbenzenes

Khatri

Han

Luong

et al. 2019

J. Org. Chem.

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Silver-Catalyzed C–H Aryloxydifluoromethylation and Arylthiodifluoromethylation of Heteroarenes

Zhu

Huang

et al. 2020

Org. Lett.

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The oxidative C–H aryloxydifluoromethylation and arylthiodifluoromethylation of heteroaromatic compounds through the decarboxylation of easily accessible aryloxydifluoroacetic acids and arylthiodifluoroacetic acids, respectively, are disclosed. These reactions are promoted by the combination of catalytic AgNO3 and Selectfluor or K2S2O8 to give ArOCF2- and ArSCF2-substituted heteroaromatic compounds in moderate to high yields.

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Single C–F Transformations of o-Hydrosilyl Benzotrifluorides with Trityl Compounds as All-in-One Reagents

et al. 2020

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A facile method to prepare difluoromethylenes, including α,αdifluorobenzyl chlorides, by single C−F transformations of benzotrifluorides is disclosed. The C−F cleavage followed by chlorination proceeded smoothly using trityl chloride through the generation of trityl cation as an activator and chloride anion as a nucleophile. Diverse difluoromethylenes such as difluorobenzyl ethers were efficiently prepared by virtue of the good versatility of the resulting chloro and fluorosilyl groups. Letter pubs.acs.org/OrgLett

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Preparation of (Phenyldifluoromethyl)- and (Phenoxydifluoromethyl)-silanes by Magnesium-Promoted Carbon-Chlorine Bond Activation

Cited by 5 publications

References 9 publications

Controlling the Cleavage of Carbon–Carbon Bonds To Generate α,α-Difluorobenzyl Carbanions for the Construction of Difluoromethylbenzenes

Controlling the Cleavage of Carbon–Carbon Bonds To Generate α,α-Difluorobenzyl Carbanions for the Construction of Difluoromethylbenzenes

Silver-Catalyzed C–H Aryloxydifluoromethylation and Arylthiodifluoromethylation of Heteroarenes

Single C–F Transformations of o-Hydrosilyl Benzotrifluorides with Trityl Compounds as All-in-One Reagents

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