Synthesis of Sterically Hindered Dialkyl Ethers via Palladium-Catalyzed Fluoro-alkoxylation of gem-Difluoroalkenes

Organic Letters, Journal Year: 2024, Volume and Issue: 26(23), P. 4953 - 4957

Published: May 30, 2024

Organofluorine compounds are of high value in medicinal and agricultural chemistry. Herein, we report a palladium-catalyzed fluoro-alkoxylation gem-difluoroalkenes for the synthesis much more challenging sterically hindered ethers. This reaction represents direct method α-trifluoromethyl ethers with broad functional group tolerance excellent regioselectivity. system employs N-fluorobenzenesulfonimide (NFSI) as an electrophilic fluorine source alcohols nucleophilic donors, including but not limited to tert-substituted alcohols.

Language: Английский

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Direct electrochemical difluorination and azo-fluorination of gem-difluorostyrenes

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 11(1), P. 142 - 148

Published: Nov. 22, 2023

A direct electrolysis protocol for difluorination and azo-fluorination of gem -difluorostyrenes was achieved involving Et 3 N·3HF as fluorine source. The electrochemical reduction the benzyl C–F bond also achieved.

Language: Английский

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Electrochemical Fluorination Functionalization of gem-Difluoroalkenes with CsF as a Fluorine Source: Access to Fluoroalkyl Building Blocks

Organic Letters, Journal Year: 2023, Volume and Issue: 26(1), P. 241 - 246

Published: Dec. 29, 2023

Using easily handled CsF as a fluorine source, an electrochemically metal-free protocol for chemo- and regioselective synthesis of various types long-chain perfluoroalkyl aromatics with gem-difluoroalkene substrate alcohol or azole additional nucleophile was developed. The eletrochemical transformation could tolerate several functional groups, such halogens, cyanos, benzyls, heterocycles, is amenable to gram-scale. application this electrochemical method in radiofluorination also tested.

Language: Английский

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Photoredox-Catalyzed gem-Difluoromethylenation of Aliphatic Alcohols with 1,1-Difluoroalkenes to Access α,α-Difluoromethylene Ethers

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(17), P. 12744 - 12754

Published: Aug. 23, 2023

A switchable synthesis of alcohols and ketones bearing a CF2-OR scaffold using visible-light promotion is described. The method PDI catalysis characterized by its ease operation, broad substrate scopes, the ability to switch between desired products without need for transition metal catalysts. addition or absence base plays key role in controlling major products.

Language: Английский

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Synthesis of α-Trifluoromethyl Alkynes through Fluoroalkynylation of gem-Difluoroalkenes

Organic Letters, Journal Year: 2023, Volume and Issue: 25(40), P. 7293 - 7297

Published: Sept. 29, 2023

A trifluoromethylalkynylation reaction of gem-difluoroalkenes with alkynyl sulfoxide by photoredox radical addition good functional group tolerance in moderate to high yields, is developed for the synthesis α-trifluoromethyl alkyne. This features simple operation and inexpensive raw materials provides an expeditious route synthesize biologically relevant fluorine-containing compounds diverse structural skeletons.

Language: Английский

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Electrochemically Direct Fluorination Functionalization of Styrenes with Different Fluorine Source: Access to Fluoroalkyl Derivatives

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(13), P. 9440 - 9449

Published: June 14, 2024

A mild protocol for electrochemically oxidative fluorodifunctionalization of styrenes has been demonstrated. The reaction proceeds under metal, external oxidant, and catalyst free conditions, allowing tunable access to a wide variety synthetically useful fluoroalkyl derivatives, such as β-fluorosulfone/fluoromethyl, fluorothiocyanation, vinylsulfonyl derivatives. Moreover, CsF was shown be the proper fluorine source this electrochemical transformation.

Language: Английский

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Electrochemically Enabled Hydroxyphosphorylation of 1,3-Enynes to Access Phosphinyl-Substituted Propargyl Alcohols

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(15), P. 10796 - 10804

Published: July 19, 2024

Catalytic difunctionalization with the direct activation of (O)P-H bonds has been recently established as a potentially robust platform to generate valuable organophosphorus compounds. In terms 1,3-enynes, despite various catalytic methods developed for hydrophosphorylation, radical-mediated hetero-functionalization two different atoms less explored. this study, we disclosed an electrochemically induced hydroxyphosphorylation 1,3-enynes construction phosphinyl-substituted propargyl alcohols. The system involves both arylphosphine oxides and oxygen in ambient air no external metal or additive needed. use electrochemistry ensures regioselective, atom-economic eco-friendly process. This strategy highlights advantages mild reaction conditions, readily available starting materials broad substrate scope, showing its practical synthetic value organic synthesis.

Language: Английский

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Pd^II/Cu^I-Cocatalyzed Radical Arylation of gem-Difluoroalkenes Using Arylsulfonyl Chlorides

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 8, 2024

A Pd

Language: Английский

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FON: An Innovative Fluorinated Group via Hydroetherification-Type Reactivity

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 17, 2024

An efficient strategy for preparing the novel O-difluoroalkylhydroxylamine fluorinated functional group, coined FON, is reported. This analogue of medicinally important β-phenethyl ether scaffolds in uniting gem-difluoro and N–O moieties synthesized one step via chemo- regioselectivity metal-free hydroetherification-type additions. As shown, this unique mode reactivity realized a diverse substrate scope applied to gram-scale synthesis site-selective deuterium incorporation. Lastly, mechanistic understanding with implications Brønsted acid catalysis offered.

Language: Английский

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Electrochemical Oxidative Cascade Cyclization of Alkenyl Alcohols with External Nucleophiles to Access Amino- and Hydroxy-Functionalized O-Heterocycles

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 20, 2024

A convenient electrochemical oxidative cascade cyclization of alkenes equipped with pendant alcohols general nucleophiles was developed. Using readily available diarylmethanimine and carboxylic acids as nucleophilic sources, a broad range internal alkene terminal substrates could produce RCO2- Ar2CN-functionalized O-heterocycles in moderate to high yields without the requirement for external oxidants metals. These resulting products can subsequently be hydrolyzed yield valuable NH2- OH-functionalized tetrahydrofurans tetrahydropyranes under mild conditions. Importantly, efficient conversion secondary alcohol amines complete inversion configuration enhances methodology, enabling construction 2-aryl-3-amino tetrahydrofuran complementary diastereoselectivity.

Language: Английский

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