Mechanical‐Force‐Induced Non‐spontaneous Dehalogenative Deuteration of Aromatic Iodides Enabled by Using Piezoelectric Materials as a Redox Catalyst

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(28)

Published: April 30, 2024

Abstract The development of green and efficient deuteration methods is great significance for various fields such as organic synthesis, analytical chemistry, medicinal chemistry. Herein, we have developed a dehalogenative strategy using piezoelectric materials catalysts in solid‐phase system under ball‐milling conditions. This non‐spontaneous reaction induced by mechanical force. D 2 O can serve both deuterium source an electron donor the transformation, eliminating need additional stoichiometric exogenous reductants. A series (hetero)aryl iodides be transformed into deuterated products with high incorporation. method not only effectively overcomes existing synthetic challenges but also used labelling drug molecules derivatives. Bioactivity experiments molecule suggest that D‐ipriflavone enhances inhibitory effects on osteoclast differentiation BMDMs vitro .

Language: Английский

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Mechanochemical Deoxyfluorination of Carboxylic Acids to Acyl Fluorides and Successive Mechanochemical Amide Bond Formation

ACS Sustainable Chemistry & Engineering, Journal Year: 2024, Volume and Issue: 12(9), P. 3565 - 3574

Published: Feb. 16, 2024

Diverse methods have been reported for the synthesis of acyl fluorides; however, an environmentally benign method fluorides remains underdeveloped. In this study, we developed solvent-free mechanochemical deoxyfluorination carboxylic acids to mediated by 1,1,2,2-tetrafluoroethyl-N,N-dimethylamine (TFEDMA) using a ball mill. This facilitated high product yields in short reaction times even sterically challenged acids. We also realized coupling and amines as well TFEDMA-mediated direct with via sequential one-pot deoxyfluorination/coupling pathway. Furthermore, protocol was expanded include peptide synthesis. The efficiency protocol, terms speed, characteristics, favorable E-factor, aligns requirements current environmental policies.

Language: Английский

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Mechanochemical Difluoromethylations of Alcohols

CCS Chemistry, Journal Year: 2023, Volume and Issue: 5(8), P. 1737 - 1744

Published: May 8, 2023

Difluoromethyl ethers are formed through mechanochemical reactions of alcohols with difluorocarbene in a mixer mill.The protocol could be applied to primary, secondary, and tertiary alcohols, yielding the corresponding products excellent yields (up 99%) after 1 h reaction time at room temperature.The transformations proceeded under solvent-free conditions, followed by product purification filtration, which drastically reduced amount waste generated during process.CsCl + TMSCF 2 Br Solvent-free Pure filtration rt, 1°, 2°, 3°alcohols Mild conditions Operationally simple Difluorocarbene pathway

Language: Английский

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Mechanochemical aerobic oxidative Heck coupling by polymer-assisted grinding: cyclodextrin additive facilitating regioselectivity control

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(10), P. 5890 - 5899

Published: Jan. 1, 2024

A novel approach utilizing the polymer-assisted grinding (POLAG) technique to facilitate regioselective oxidative Heck coupling of aryl boronic acids with electronically unbiased olefins under solvent-free conditions was presented.

Language: Английский

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Advances in the Synthetic Utility of Difluorocarbene Generated from TMSCF₃ (Ruppert‐Prakash Reagent) and Its Derivatives

The Chemical Record, Journal Year: 2025, Volume and Issue: unknown

Published: March 12, 2025

Abstract Organofluorine compounds are of pivotal significance particularly, in drug and agrochemical industries different strategies have been designed for their synthesis. The last two decades witnessed the emergence difluorocarbene as an efficient synthetic tool, providing easy access to organofluorine compounds. This review summarises reactions generated from Ruppert‐Prakash reagent (TMSCF 3 ) its derivatives TMSCF 2 Cl Br. Among various fluorination techniques available, chemistry offers a cost effective procedure, opening avenue large number details developments utility derivatives, till date.

Language: Английский

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Electrochemical Access to Difluoromethyl Groups: An Overview of Scope, Mechanisms, and Challenges

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 6826 - 6851

Published: April 14, 2025

Language: Английский

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Ball‐Milling‐Promoted Copper‐Catalyzed Solid‐State Radical C–H Difluoroalkylation Reactions

ChemistryEurope, Journal Year: 2025, Volume and Issue: unknown

Published: April 17, 2025

A mechanochemical strategy for promoting copper‐catalyzed solid‐state radical C–H difluoroalkylation reactions has been devised. Compared to traditional solution‐based methods, this mechanoredox approach offers enhanced ease of handling, greater cleanliness, and improved sustainability the synthesis difluoroalkylated indoles, which constitute crucial structural motifs in contemporary drug discovery. The underlying reaction mechanism is investigated through meticulous step‐by‐step control experiments that highlighted substantial influence conditions. versatility protocol demonstrated by its applications complex natural products derivatives.

Language: Английский

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Accessing Structurally Diverse Aryl Difluoromethyl Ethers with Bromo(difluoro)acetic Acid

Chemical Communications, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

We report a new streamlined approach for the difluoromethylation of ubiquitous phenols using inexpensive bromo(difluoro)acetic acid, yielding wide array structurally diverse OCF

Language: Английский

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Mechanochemical difluoromethylation of (thio)phenols and N‐heterocycles

Israel Journal of Chemistry, Journal Year: 2023, Volume and Issue: 63(10-11)

Published: Sept. 13, 2023

Abstract Herein, we report a minimalistic protocol for the solvent‐free, mechanochemical difluoromethylation of (thio)phenols and N ‐heteroarenes using non‐ozone depleting chlorodifluoromethyl phenyl sulfone as difluorocarbene source. This features short reaction time, excellent functional group tolerance, compatibility with complex biologically active scaffolds.

Language: Английский

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Fluorinated Chiral Pyrans Obtained via Mechanochemical Organocatalytic Michael/oxa‐Michael Cascade

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

Published: June 3, 2024

Abstract Fluorine‐containing compounds are important in medicine or crop‐protection. Herein, we show asymmetric organocatalytic Michael/oxa‐Michael cascade leading to chiral fluorinated pyrans under mechanochemical conditions. Formal oxa‐Diels‐Alder reaction between fluorine containing unsaturated keto esters and β,γ‐unsaturated ketones afforded a range of drug‐like pyran derivatives short times good high yields. Ball‐milling conveys the product yields, while keeping enantiomeric purities products. The is diastereodivergent depending on use either monofunctional amine catalysts bifunctional thiourea squaramide.

Language: Английский

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