1.5 Radical Trifluoromethylation DOI
Pinhong Chen, Guosheng Liu

Published: Jan. 1, 2024

Abstract The development of methods for the introduction a trifluoromethyl group into organic molecules has been quite prominent over last three decades. Among these methods, radical trifluoromethylation gained renewed interest, and exhibits mild conditions together with good substrate compatibility selectivity involvement photo-, electro-, metal-catalysis. In this review, summary efforts is presented in two types reaction pathways. first addition to unsaturated moieties such as alkenes, alkynes, (het)arenes. second ordinary carbon-centered radicals, including alkyl, alkenyl, aryl radicals.

Language: Английский

The Role of Small Molecules Containing Fluorine Atoms in Medicine and Imaging Applications DOI Creative Commons

Emily Henary,

Stefanie Casa, Tyler L. Dost

et al.

Pharmaceuticals, Journal Year: 2024, Volume and Issue: 17(3), P. 281 - 281

Published: Feb. 22, 2024

The fluorine atom possesses many intrinsic properties that can be beneficial when incorporated into small molecules. These include the atom’s size, electronegativity, and ability to block metabolic oxidation sites. Substituents feature fluorine-containing groups are currently prevalent in drugs lower cholesterol, relieve asthma, treat anxiety disorders, as well improve chemical of various medications imaging agents. dye scaffolds (fluorescein/rhodamine, coumarin, BODIPY, carbocyanine, squaraine dyes) reported will address incorporation scaffold contribution it provides its application an agent. It is also important recognize radiolabeled atoms used for PET early detection diseases. This review discuss benefits incorporating molecules give examples fluorinated pharmaceutical industry techniques.

Language: Английский

Citations

21
O‐Trifluoromethylation of Carboxylic Acids via the Formation and Activation of Acyloxy(phenyl)trifluoromethyl‐λ3‐Iodanes DOI
Hongye Zhu, Chi Gao, Ting Yu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(16)

Published: Feb. 27, 2024

Abstract Here we report the challenging O‐trifluoromethylation of carboxylic acids via formation and activation acyloxy(phenyl)trifluoromethyl‐λ 3 ‐iodanes. The method provides an easy access to various potentially valuable hitherto elusive trifluoromethyl esters. A remarkably wide range substrates with commonly encountered functional groups are compatible this reaction, including aromatic aliphatic acids, as well Food Drug Administration (FDA) approved drugs pharmaceutically relevant molecules. reaction mechanism origins enhanced reactivity by zinc chloride (ZnCl 2 ) were discussed from experimental evidence density theory (DFT) calculation.

Language: Английский

Citations

4
BINAP‐Accelerated Photoinduced Trifluoromethylation of (Hetero)Aryl Iodides DOI Open Access

Xueyan Yang,

Yan Kang, Hai‐Shu Lin

et al.

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

Published: March 6, 2025

Abstract Trifluoromethyl groups hold significance in the bioactivity and physical properties of organic molecules. Contemporary approaches to trifluoromethylated aromatics typically involve coupling CuCF 3 reagents with aryl halides, which is limited by difficulty oxidative addition copper organohalides. Herein, a photoinduced ligand‐catalyzed trifluoromethylation/pentafluoroethylation (hetero)aryl iodides presented. The conversion C─I bond into C─CF enabled photochemistry copper, produces radicals situ generated from Ruppert–Prakash reagent under visible light. This radical approach circumvents challenge catalytic amount rac ‐BINAP substantially accelerates whole process, allowing reaction complete within 1 h very mild conditions without using any additional photo‐redox catalysts. readily availability starting material, high efficiency, broad utility make this transformation attractive for practitioners synthetic medicinal chemistry.

Language: Английский

Citations

0
Organic Peroxides in Transition-Metal-Free Cyclization and Coupling Reactions (C–C) via Oxidative Transformation DOI Creative Commons
Amin Rezaeifard, Fatemeh Doraghi, Fatemeh Akbari

et al.

ACS Omega, Journal Year: 2025, Volume and Issue: unknown

Published: April 14, 2025

Transition-metal-free transformations are recognized as green and sustainable methods for constructing carbon-carbon bonds in organic synthesis. This review describes the application of six peroxides, including tert-butyl hydroperoxide (TBHP), di-tert-butyl peroxide (DTBP), peroxybenzoate (TBPB), benzoyl (BPO), dialauroyl (DLP), diguyl (DCP), C-C bond construction, highlighting selected examples mechanisms challenging transformations. Each section concludes with a detailed overview suitable reagents various coupling reactions strengths weaknesses reported works. work aims to inspire further innovations transition-metal-free oxidative transformations, promoting eco-friendly chemical processes paving way new peroxide-based synthesis methods.

Language: Английский

Citations

0
Enantioselective Desymmetrization of Trifluoromethylated Tertiary Benzhydrols via Hydrogen-Acceptor-Free Ir-Catalyzed Dehydrogenative C–H Silylation: Decisive Role of the Trifluoromethyl Group DOI Creative Commons
Yoshihiko Yamamoto,

Ryu Tadano,

Takeshi Yasui

et al.

JACS Au, Journal Year: 2024, Volume and Issue: 4(2), P. 807 - 815

Published: Feb. 15, 2024

Although the trifluoromethyl (CF3) group is one of most important fluorinated groups owing to its significant ability modulate pharmacological properties, constructing trifluoromethylated stereogenic centers in an enantioselective manner has been a formidable challenge. Herein, we report development desymmetrization benzhydrols via intramolecular dehydrogenative silylation using Ir catalysts with chiral pyridine-oxazoline (PyOX) ligands. The produced benzoxasilol was transformed into several unsymmetrical iododesilylation and subsequent transition-metal-catalyzed cross-coupling reactions. Moreover, same catalyst system used for kinetic resolution benzhydrols.

Language: Английский

Citations

3
Copper-Catalyzed Synthesis of 4-CF3-1,2,3-Triazoles: An Efficient and Facile Approach via Click Reaction DOI Creative Commons

Tinghong Tang,

Cuiting Chen,

Xin Fu

et al.

Molecules, Journal Year: 2024, Volume and Issue: 29(6), P. 1191 - 1191

Published: March 7, 2024

Incorporation of a trifluoromethyl group with 1,2,3-triazoles motifs was described. We explored click reaction approach for regioselective synthesis 1-susbstituted-4-trifluoromethyl-1,2,3-triazoles in which 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) reacts commercial 2-bromo-3,3,3-trifluoropropene (BTP) to form 3,3,3-trifloropropyne (TFP) situ. Arising from merits associated the availability and stability BTP, high efficiencies CuI/1,10-Phenanthroline (Phen)-catalyzed cycloaddition reactions azides alkynes, this readily performed process takes place target yields, wide azide substrate scope. The potential value protocol demonstrated by its application gram-scale reaction.

Language: Английский

Citations

2
Studies on fluorofunctionalization of some functionalized alkene scaffolds DOI Creative Commons
Tamás T. Novák,

Klára Aradi,

Ágnes Gömöry

et al.

Results in Chemistry, Journal Year: 2024, Volume and Issue: 7, P. 101309 - 101309

Published: Jan. 1, 2024

A study on some halofluorination and fluoroselenation protocols of various functionalized cyclic olefins, such as esters, lactams or amino esters model compounds is presented. The ring olefin bond functionalizations were based their activation either with NBS, NIS PhSeBr followed by treatment nucleophilic fluorinating agents, Deoxo-Fluor. attempted synthetic assays have been found to be highly substrate dependent, influenced the nature functional groups present cycloalkene skeleton well stereostructural architecture starting compounds.

Language: Английский

Citations

1
Understanding and Controlling Fluorinated Diacyl Peroxides and Fluoroalkyl Radicals in Alkene Fluoroalkylations DOI Creative Commons
Shintaro Kawamura, Mikiko Sodeoka

The Chemical Record, Journal Year: 2023, Volume and Issue: 23(9)

Published: July 31, 2023

Abstract The demand for practical methods the synthesis of novel fluoroalkyl molecules is increasing owing to their diverse applications. Our group has achieved efficient difunctionalizing fluoroalkylations alkenes using fluorinated carboxylic anhydrides as user‐friendly sources. Fluorinated diacyl peroxide, prepared in situ from anhydrides, enables development reactions when used a radical fluoroalkylating reagent. In this account, we aim provide an in‐depth understanding structure, bonding, and reactivity peroxides radicals well control fluoroalkylation reactions. first part physical properties are described. subsequent part, categorize into copper‐catalyzed metal‐free utilizing oxidizing peroxides. We also outline examples mechanisms.

Language: Английский

Citations

3
Iodonium based regioselective double nucleophilic alkene functionalization of a hydrofluoroolefin scaffold DOI

János T. Csenki,

Zoltán Novàk

Chemical Communications, Journal Year: 2023, Volume and Issue: 60(6), P. 726 - 729

Published: Dec. 12, 2023

Regioselective heterodifunctionalization of a hydrofluoroolefin (HFO-1234yf) scaffold was developed for the construction diverse molecular frameworks via fluoroalkenyliodonium salt.

Language: Английский

Citations

2
O‐Trifluoromethylation of Carboxylic Acids via the Formation and Activation of Acyloxy(phenyl)trifluoromethyl‐λ3‐Iodanes DOI
Hongye Zhu, Chi Gao,

Ting Yu

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(16)

Published: Feb. 27, 2024

Abstract Here we report the challenging O‐trifluoromethylation of carboxylic acids via formation and activation acyloxy(phenyl)trifluoromethyl‐λ 3 ‐iodanes. The method provides an easy access to various potentially valuable hitherto elusive trifluoromethyl esters. A remarkably wide range substrates with commonly encountered functional groups are compatible this reaction, including aromatic aliphatic acids, as well Food Drug Administration (FDA) approved drugs pharmaceutically relevant molecules. reaction mechanism origins enhanced reactivity by zinc chloride (ZnCl 2 ) were discussed from experimental evidence density theory (DFT) calculation.

Language: Английский

Citations

0