Wonderful fusion of organofluorine chemistry and decarboxylation strategy

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(10), P. 6094 - 6151

Published: Jan. 1, 2021

Decarboxylation strategy has been emerging as a powerful tool for the synthesis of fluorine-containing organic compounds that play important roles in various fields such pharmaceuticals, agrochemicals, and materials science. Considerable progress decarboxylation made over past decade towards construction diverse valuable fluorinated fine chemicals which part can be brought two ways. The first way is described reaction non-fluorinated carboxylic acids (and their derivatives) with fluorinating reagents, well building blocks. second dedicated to exploration use decarboxylative transformations. This review aims provide comprehensive summary development applications radical, nucleophilic cross-coupling strategies organofluorine chemistry.

Language: Английский

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Copper-Catalyzed Decarboxylative Difluoromethylation

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(29), P. 11398 - 11403

Published: July 8, 2019

We report herein a highly efficient Cu-catalyzed protocol for the conversion of aliphatic carboxylic acids to corresponding difluoromethylated analogues. This robust, operationally simple and scalable tolerates variety functional groups can convert diverse array acid-containing complex molecules alkyl-CF2H products. Mechanistic studies support involvement alkyl radicals.

Language: Английский

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Silver‐Catalyzed Decarboxylative Allylation of Difluoroarylacetic Acids with Allyl Sulfones in Water

Chemistry - An Asian Journal, Journal Year: 2020, Volume and Issue: 15(7), P. 1175 - 1179

Published: Feb. 14, 2020

A practical silver-catalyzed decarboxylative allylation of α,α-difluoroarylacetic acids with allyl sulfones is described, which provides a variety β,β-difluorinated alkenes in good yields. Notably, the reaction proceeds smoothly water functional group tolerance. The practicality and synthetic value this process was demonstrated by scaled-up experiment elaboration products via reduction or Heck reaction. Primary mechanism investigations suggest that radical might be involved.

Language: Английский

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Silver‐Enabled General Radical Difluoromethylation Reaction with TMSCF₂H

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 60(8), P. 4300 - 4306

Published: Nov. 16, 2020

Abstract A silver‐mediated oxidative difluoromethylation of styrenes and vinyl trifluoroborates with TMSCF 2 H is reported for the first time. This method enables direct facile access to CF H‐alkenes from abundant alkenes excellent functional‐group compatibility. Moreover, this Ag/TMSCF protocol could further enable a series radical reactions wide array substrates, offering generic complementary platform construction diversified C−CF bonds.

Language: Английский

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Modern approaches towards the synthesis of geminal difluoroalkyl groups

Organic & Biomolecular Chemistry, Journal Year: 2021, Volume and Issue: 19(5), P. 947 - 964

Published: Jan. 1, 2021

This review will cover the importance of and most recent approaches toward geminal difluoroalkyl groups using transition metal-mediated, photochemical, organocatalytic, other methods.

Language: Английский

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Introduction of the difluoromethyl group at the meta- or para-position of pyridines through regioselectivity switch

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: May 15, 2024

Abstract Difluoromethyl pyridines have gained significant attention in medicinal and agricultural chemistry. The direct C−H-difluoromethylation of represents a highly efficient economic way to access these azines. However, the meta-difluoromethylation has remained elusive methods for site-switchable regioselective meta- para-difluoromethylation are unknown. Here, we demonstrate meta-C−H-difluoromethylation through radical process by using oxazino pyridine intermediates, which easily accessed from pyridines. selectivity can be readily switched para situ transformation pyridinium salts upon acid treatment. preparation various para-difluoromethylated this approach is presented. mild conditions used also allow late-stage or containing drugs. Sequential double functionalization presented, further underlines value work.

Language: Английский

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Recent Progress on the Synthesis of CF2H-Containing Derivatives

Synthesis, Journal Year: 2019, Volume and Issue: 51(24), P. 4549 - 4567

Published: Sept. 30, 2019

Recent years have witnessed a growing interest in the development of novel synthetic methods and new reagents for synthesis difluoromethylated compounds. Dozens studies been published on this topic each year over past few years. These are focused direct indirect difluoromethylation various organic functionalities via nucleophilic-, electrophilic-, radical-, carbene- or metal-mediated mechanisms. The present short review covers very recent studies, between mid-2017 early 2019, compounds containing CF2H group. A brief summary physicochemical properties medicinal applications is also included. 1 Introduction 2 Nucleophilic Difluoromethylation 2.1 Metal-Mediated 2.2 Non-Metal Difluoromethyl Nucleophiles 3 Radical 3.1 Metal-Induced 3.2 Non-Metal-Induced 3.3 Electrochemically Induced 4 Carbene-Based 4.1 Carbene 4.2 Carbenes 5 Cross-Coupling 5.1 Palladium-Catalyzed 5.2 Nickel-Catalyzed 5.3 Copper-Mediated 5.4 Iron-Catalyzed 5.5 Gold-Mediated 6 Electrophilic 7 Other Examples 7.1 Difluoromethyl-Borane Complex 7.2 Tellurium Derivative 8 Summary

Language: Английский

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Late‐Stage ¹⁸ F‐Difluoromethyl Labeling of N‐Heteroaromatics with High Molar Activity for PET Imaging

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(37), P. 13149 - 13154

Published: July 19, 2019

Despite a growing interest in CHF2 medicinal chemistry, there is lack of efficient methods for the insertion CHF18 F into druglike compounds. Herein described photoredox flow reaction 18 F-difluoromethylation N-heteroaromatics that are widely used chemistry. Following two-step synthesis new reagent, completed within two minutes and proceeds by C-H activation, circumventing need pre-functionalization substrate. The method operationally simple affords straightforward access to radiolabeled with high molar activity suitable biological vivo studies clinical application.

Language: Английский

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Visible light photocatalytic acyldifluoroalkylation of unactivated alkenes for the direct synthesis of gem-difluorinated ketones

Organic Chemistry Frontiers, Journal Year: 2019, Volume and Issue: 6(7), P. 1022 - 1026

Published: Jan. 1, 2019

A photoredox-catalyzed alkene acyldifluoroalkylation with difluoroacetic acids for the direct synthesis of gem-difluorinated cyclic ketones is developed.

Language: Английский

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Nickel-Catalyzed Decarbonylative Synthesis of Fluoroalkyl Thioethers

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(15), P. 8315 - 8320

Published: July 17, 2020

This report describes the development of a nickel-catalyzed decarbonylative reaction for synthesis fluoroalkyl thioethers (RFSR) from corresponding thioesters. Readily available, inexpensive, and stable carboxylic acids (RFCO2H) serve as (RF) source in this transformation. Stoichiometric organometallic studies reveal that RF–S bond-forming reductive elimination is challenging step catalytic cycle. led to identification diphenylphosphinoferrocene optimal ligand Ultimately, method was applied construction diverse (RFSR), with R = both aryl alkyl.

Language: Английский

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