Recent Advance in the C−F Bond Functionalization of Trifluoromethyl Aromatic and Carbonyl Compounds

ChemCatChem, Год журнала: 2023, Номер 16(8)

Опубликована: Дек. 28, 2023

Abstract The selective C−F bonds functionalization in available trifluoromethyl compounds is an economic route for obtaining high‐value organic fluorine compounds. However, due to the high dissociation energy group, strength of bond decreases continuously during defluorination, posing a challenge modifying such molecules without over‐conversion. Over past few years, there has been significant progress developing efficient methods constructing difluoromethylene unit, using approaches as radical chemistry, photochemistry, electrochemistry, and organometallic chemistry. These involve difluorocarbon radicals, cations, anions, carbenes intermediates. In this review, we summarized recent five years research achievements field single cleavage aromatic carbonyl gain diverse difluoromethylene‐containing via different intermediate strategies.

Язык: Английский

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New Opportunities to Access Fluorinated Molecules Using Organophotoredox Catalysis via C(sp³)–F Bond Cleavage

JACS Au, Год журнала: 2025, Номер 5(2), С. 466 - 485

Опубликована: Фев. 7, 2025

Fluorinated molecules are of paramount importance because their unique properties. As a result, the search for innovative approaches to synthesis this class compounds has been relentless over years. Among these, combination photocatalysis and organofluorine chemistry turned out be an effective partnership access unattainable fluorinated molecules. This Perspective provides overview recent advances in synthesizing via organophotoredox-catalyzed defluorination process from trifluoromethylated compounds. It encompasses preparation difluoromethylated (hetero)arenes, amides, esters as well gem-difluoroalkene derivatives using C(sp3)–F bond activation or β-fragmentation. will highlight remaining challenges discuss future research opportunities.

Язык: Английский

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Visible Light Induced Selective Cleavage of Single C(sp3)-F Bond in Trifluoromethyl Groups Containing Compounds

Tetrahedron, Год журнала: 2024, Номер 163, С. 134155 - 134155

Опубликована: Июль 16, 2024

Язык: Английский

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Mechanistic Exploration of N-Heterocyclic Carbene Boranes as the Hydrogen Atom Transfer Reagent in Selective Hydrodefluorination Reactions

ACS Catalysis, Год журнала: 2024, Номер unknown, С. 17547 - 17555

Опубликована: Ноя. 13, 2024

In the modern era of organic synthesis, mechanisms centered on radical intermediates have become increasingly impactful. Among all these, hydrogen atom transfer (HAT) represents one most fundamental chemical reaction steps and has found applications in designing practical transformations. Herein, we present a detailed case study selective hydrodefluorination trifluoromethylarenes utilizing N-heterocyclic carbene boranes (NHC-boranes) as donor. Under optimal conditions featuring an acridine-based photocatalyst, complete selectivity for mono-hydrodefluorination was achieved across wide array substrates. Comprehensive mechanistic studies combining experimental computational approaches disproved chain process involving fluorine but rather pointed to HAT non-chain mechanism, where key step involves difluorobenzylic abstracting from NHC-borane generate boryl polarity-matched fashion. Evaluation selection Lewis base-ligated revealed molecular descriptors critical outcomes this reaction, classification model built explain structure–reactivity relationship how various elementary can be influenced. These results collectively provide valuable information future design increase utility chemistry.

Язык: Английский

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Defluorinative Haloalkylation of Unactivated Alkenes Enabled by Dual Photoredox and Copper Catalysis

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(18), С. 13518 - 13529

Опубликована: Сен. 10, 2024

A three-component defluorinative haloalkylation of alkenes with trifluoromethyl compounds and TBAX (X = Cl, Br) via dual photoredox/copper catalysis is reported. The mild conditions are compatible a wide array activated aromatics bearing diverse substituents, various nonactivated terminal internal alkenes, enabling straightforward access to synthetically valuable γ-gem-difluoroalkyl halides high efficiency. Mechanistic studies indicate that the [Cu] complexes not only serve as XAT catalysts but also facilitate SET reduction groups by photocatalysts. Additionally, resulting alkyl halide products can versatile conversion intermediates for synthesis range compounds.

Язык: Английский

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Unveiling the Selectivity of Ru(II)-Catalyzed C–H Activation for Defluorinative Cyclization of 2-Arylbenzimidazole and Trifluoromethyl Diazo: A DFT Study

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(11), С. 7982 - 7990

Опубликована: Май 28, 2024

The synthesis of monofluorinated heterocyclic compounds by C-H activation combined with defluorination is useful. Studies on the reaction mechanism and selectivity have shown that these processes play a positive role in promoting development reactions. Density functional theory (DFT) calculations were performed to investigate Ru(II)-catalyzed 2-arylbenzimidazole trifluoromethyl diazo. DFT showed occurs through concerted metalation/deprotonation (CMD) mechanism. After that, deprotonation defluorinative cyclization are assisted acetate trifluoroethanol (TFE). Further mechanistic insights noncovalent interaction (NCI) analysis also obtained elucidate origin process.

Язык: Английский

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BINOLates as potent reducing photocatalysts for inert bond activation and reduction of unsaturated systems

Chem, Год журнала: 2024, Номер unknown

Опубликована: Дек. 1, 2024

Язык: Английский

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An Nadh Model (10-Benzyl-9,10-Dihydroacridine) Enabled Radical Borylation of C(Sp2)−X Bonds

Опубликована: Янв. 1, 2024

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Язык: Английский

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An NADH model (10-benzyl-9,10-dihydroacridine) enabled radical borylation of C(sp2)–X bonds

Tetrahedron Letters, Год журнала: 2024, Номер 143, С. 155116 - 155116

Опубликована: Май 21, 2024

Язык: Английский

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