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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Reactivities of electrophilic N–F fluorinating reagents

Chemical Communications, Journal Year: 2020, Volume and Issue: 57(6), P. 683 - 712

Published: Dec. 24, 2020

A comprehensive review of past and present approaches towards qualitative quantitative rankings the reactivities electrophilic fluorinating agents.

Language: Английский

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Visible-Light-Induced Decarboxylative Fluorination of Aliphatic Carboxylic Acids Catalyzed by Iron

Organic Letters, Journal Year: 2022, Volume and Issue: 24(32), P. 5972 - 5976

Published: Aug. 11, 2022

An efficient and inexpensive protocol for the direct decarboxylative fluorination of aliphatic carboxylic acids catalyzed with iron salts under visible light is presented. This new method allows facile a diverse array even on gram scale using Schlenk flask without loss efficiency. Mechanistic studies suggest that photoinduced ligand-to-metal charge transfer process enables generation key step to generate carboxyl radical intermediates.

Language: Английский

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Site-Selective Late-Stage C–H Functionalization via Thianthrenium Salts

Synlett, Journal Year: 2021, Volume and Issue: 33(04), P. 339 - 345

Published: April 13, 2021

Abstract The high abundance of C–H bonds in organic molecules makes functionalization a powerful approach to quickly increase the complexity an molecule. However, also provides challenge reactions: selectivity. While most reactions produce mixtures different products for substrates, we have developed highly selective method aromatic via sulfonium salts. reaction does not require certain directing group be selective. introduced functional is group, which participates various follow-up such as palladium-catalyzed cross-coupling and photoredox catalysis. Here discuss our pathway develop well its scope utility. 1 Introduction 2 Site-Selective Synthesis Sulfonium Salts 3 Palladium-Catalyzed Cross-Coupling 4 Photoredox Catalysis 5 Sulfur(IV) Reductive Elimination 6 Cine Substitution 7 Conclusion

Language: Английский

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Hydrogen Bonding Phase-Transfer Catalysis with Alkali Metal Fluorides and Beyond

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(12), P. 5200 - 5213

Published: March 16, 2022

Phase-transfer catalysis (PTC) is one of the most powerful catalytic manifolds for asymmetric synthesis. Chiral cationic or anionic PTC strategies have enabled a variety transformations, yet studies on use insoluble inorganic salts as nucleophiles synthesis enantioenriched molecules remained elusive. A long-standing challenge development methods carbon-fluorine bond formation from readily available and cost-effective alkali metal fluorides. In this Perspective, we describe how H-bond donors can provide solution through fluoride binding. We examples, primarily our own research, to discuss hydrogen bonding interactions impact reactivity role phase-transfer catalysts bring solid-phase fluorides in solution. These led (HB-PTC), new concept PTC, originally crafted but offering opportunities beyond enantioselective fluorination. Looking ahead, unlimited options that consider diversify donor, salt, electrophile, herald era catalysis. Whether abundant lattice energy significantly higher than those studied date could be considered nucleophiles, e.g., CaF2, remains an open question, with solutions may found synergistic PTC.

Language: Английский

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Handling fluorinated gases as solid reagents using metal-organic frameworks

Science, Journal Year: 2023, Volume and Issue: 381(6665), P. 1455 - 1461

Published: Sept. 28, 2023

Fluorine is an increasingly common substituent in pharmaceuticals and agrochemicals because it improves the bioavailability metabolic stability of organic molecules. Fluorinated gases represent intuitive building blocks for late-stage installation fluorinated groups, but they are generally overlooked require use specialized equipment. We report a general strategy handling as benchtop-stable solid reagents using metal-organic frameworks (MOFs). Gas-MOF prepared on gram-scale used to facilitate fluorovinylation fluoroalkylation reactions. Encapsulation gas-MOF within wax enables stable storage benchtop controlled release into solution upon sonication, which represents safer alternative gas directly. Furthermore, our approach high-throughput reaction development with these gases.

Language: Английский

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Diastereoselective Synthesis of Monofluorocyclohexenes through Photocatalyzed Cascade Cyclization of gem‐Difluoroalkenes and α,β‐Unsaturated Carbonyl Compounds

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(20)

Published: March 16, 2023

Monofluoroalkenes are nonhydrolyzable mimetics of amides. Previous work focused on the synthesis non-cyclic monofluoroalkenes. However, diastereoselective monofluorocyclohexenes from substrates is challenging. Herein, we report first photocatalyzed cascade cyclization reactions readily available α,β-unsaturated carbonyl compounds and gem-difluoroalkenes for highly functionalized monofluorocyclohexenes. The reaction shows broad substrate scope with high diastereoselectivity (>30 examples, up to 86 % yield, >20 : 1 dr). post-reaction transformations products demonstrate synthetic potential this methodology.

Language: Английский

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Recent Advances in Nonprecious Metal Catalysis

Organic Process Research & Development, Journal Year: 2023, Volume and Issue: 27(3), P. 423 - 447

Published: Feb. 17, 2023

Nonprecious-metal-catalyzed alternatives to powerful precious metal transformations are of increasing interest in academia and the pharmaceutical industry due lower cost, better sustainability, toxicity. With continual growth broad field nonprecious catalysis (NPMC), we have chosen highlight selected articles published from March June 2022 which intended examples NPMC that feel may be especially relevant development. We aim inspire academic industrial innovation through discussion herein.

Language: Английский

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eFluorination Using Cheap and Readily Available Tetrafluoroborate Salts

Organic Letters, Journal Year: 2023, Volume and Issue: 25(9), P. 1353 - 1358

Published: March 1, 2023

A practical electrochemical method for the rapid, safer, and mild synthesis of tertiary hindered alkyl fluorides from carboxylic acids has been developed without need hydrofluoric acid salts or non-glass reactors. In this anodic fluorination, collidinium tetrafluoroborate acts as both supporting electrolyte fluoride donor. wide range functional groups shown to be compatible, possibility scale-up using flow electrochemistry also demonstrated.

Language: Английский

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Iron photocatalysis via Brønsted acid-unlocked ligand-to-metal charge transfer

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

Published: July 20, 2024

Abstract Reforming sustainable 3d-metal-based visible light catalytic platforms for inert bulk chemical activation is highly desirable. Herein, we demonstrate the use of a Brønsted acid to unlock robust and practical iron ligand-to-metal charge transfer (LMCT) photocatalysis multifarious haloalkylcarboxylates (C n X m COO − , = F or Cl) produce C radicals. This process enables fluoro-polyhaloalkylation non-activated alkenes by combining easily available Selectfluor as fluorine source. Valuable alkyl fluorides including potential drug molecules can be obtained through this protocol. Mechanistic studies indicate that real light-harvesting species may derive from in situ-assembly Fe 3+ H + acetonitrile solvent, which indeed increases efficiency LMCT between center via hydrogen-bond interactions. We anticipate acid-unlocked platform would an intriguing option execute compounds.

Language: Английский

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