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

JACS Au, Journal Year: 2025, Volume and Issue: 5(2), P. 466 - 485

Published: Feb. 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.

Language: Английский

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Visible-Light-Induced Synergistic W/Cr Catalyzed gem-Difluoroallylation of Unactivated Alkanes

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 19, 2025

Currently, the scope of Nozaki-Hiyama-Kishi (NHK) reaction is limited to aldehydes and ketones construct alcohol derivatives. Herein, we have described a visible-light-induced synergistic W/Cr(III)-catalyzed NHK-type gem-difluoroallylation unactivated cyclic linear alkanes. The merits feedstock materials, mild conditions, wide functionality tolerance. Mechanistic studies imply favorable reduction CrCl3 CrCl2 by reduced decatungstate W10O325-, thus closing catalytic cycle.

Language: Английский

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Photocatalyzed/Base-Mediated Defluorinative Three-Component Cascade Cyclization: Access to Monofluorocyclohexenes and 6-Fluoro-1,2,3,4-tetrahydropyridines

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 19, 2025

A three-component cascade cyclization of α-CF3 alkenes, electron-rich and dimethyl esters or sulfonamides via a dual C–F bond cleavage process is described. This methodology provides general efficient strategy to access monofluorocyclohexenes 6-fluoro-1,2,3,4-tetrahydropyridines by switching the bifunctional reagents (dimethyl sulfonamides), which are valuable building blocks in synthetic chemistry pharmaceutical industries. The reaction mechanism applications products have been demonstrated.

Language: Английский

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Diastereoselective Formal [3+3] Cascade Cyclization towards Fused 4‐Fluoroalkylated 3,4‐Dihydro‐2H‐pyrans via Copper Catalysis

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 25, 2025

Comprehensive Summary The cycloaddition and annulation reactions offer a powerful method toward various important substituted 3,4‐dihydro‐2 H ‐pyran architectures. Nevertheless, the transformation for preparing fused‐polycyclic ones still remains challenging yet highly desirable until now. Herein, we report novel formal [3+3] cascade cyclization reaction to provide lactam‐fused 4‐fluoroalkylated 3,4‐dihydropyran skeletons bearing three contiguous tertiary carbon centers via copper catalysis. Of note, these annulations proceeded in an exclusively diastereoselective manner through successive inert C(sp 2 )‐Cl 3 )‐H functionalization, which exhibited site‐selectivity stereoselectivity. Additionally, evaluations on biological activities of obtained products revealed that several display inhibitory activity against Siha H1975 cancer cell lines.

Language: Английский

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Photoinduced synthesis of C2-linked phosphine oxides via radical difunctionalization of acetylene

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(18), P. 7253 - 7258

Published: Jan. 1, 2023

A photocatalyzed radical difunctionalization of acetylene was achieved, which enables the green synthesis C2-linked phosphine oxides.

Language: Английский

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Combining Hydrodefluorination and Defluorophosphorylation for Chemo- and Stereoselective Synthesis of gem-Fluorophosphine Alkenes

Organic Letters, Journal Year: 2023, Volume and Issue: 25(34), P. 6368 - 6373

Published: Aug. 18, 2023

A chemo-, regio-, and stereoselective reaction of trifluoromethyl enones, phenylsilane, phosphine oxides through a sequential hydrodefluorination defluorophosphorylation relay is developed for the synthesis distinctive gem-fluorophosphine alkenes. This multicomponent occurred under transition-metal-free conditions with good functional group tolerance. Moreover, preinstalled carbonyl auxiliary important tuning reactivity β-trifluoromethyl thereby enabling controllable selective functionalization two fluorine atoms in trifluoromethylated enones.

Language: Английский

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Synthesis of 2‐(β‐Trifluoromethyl‐β‐arylethylthio)pyridine through DBU‐Mediated Regioselective Addition of Pyridine‐2(1H)‐thione Onto α‐(Trifluoromethyl)styrenes

Asian Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 13(3)

Published: Jan. 8, 2024

Abstract An efficient and practical method for the synthesis of (β‐trifluoromethyl‐β‐aryl)ethyl 2‐pyridyl thioethers via hydrothiolation α‐(trifluoromethyl)styrenes with pyridine‐2(1 H )‐thione was reported. The reaction proceeded smoothly regioselectively in an anti‐Markovnikov manner assistance DBU afforded a variety trifluoromethyl‐containing moderate to good yields.

Language: Английский

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Photoredox Catalyzed [3 + 2]-Annulation Reaction of Pyridinium 1,4-Zwitterionic Thiolates with Alkenes: Synthesis of Dihydrothiophenes

Organic Letters, Journal Year: 2023, Volume and Issue: 25(33), P. 6105 - 6109

Published: Aug. 16, 2023

Pyridinium 1,4-zwitterionic thiolates are usually used to develop ionic annulation reactions. However, radical reactions were rare. We developed a photoredox catalyzed [3 + 2]-annulation reaction of pyridinium with alkenes, disclosed the new reactivity thiolate, and provided synthetic method for dihydrothiophene.

Language: Английский

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Solvent-Controllable C–F Bond Activation for Masked Formylation of α-Trifluoromethyl Alkenes via Organo-Photoredox Catalysis

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 89(1), P. 624 - 632

Published: Dec. 20, 2023

A solvent-controllable organo-photoredox-catalyzed C–F bond activation for masked formylation of α-trifluoromethyl alkenes with low-priced 1,3-dioxolane as formyl radical equivalent has been described. Consequently, a diversity formylated gem-difluoroalkenes and monofluoroalkenes are constructed in moderate to high yields. This approach merits readily available starting materials, mild reaction conditions, broad substrate scope. The feasibility this highlighted by the one-pot formylation/hydrolysis sequence form γ,γ-difluoroallylic aldehydes late-stage modification pharmaceutical natural product derivatives.

Language: Английский

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Base-Mediated Regioselective [3 + 3] Annulation of Alkylidene Malononitriles with Trifluoromethyl Alkenes via Dual C–F Bond Cleavage

Organic Letters, Journal Year: 2024, Volume and Issue: 26(35), P. 7452 - 7456

Published: Aug. 26, 2024

A base-mediated regioselective [3 + 3] annulation of alkylidene malononitriles with trifluoromethyl alkenes was described. The reaction proceeds through sequential intermolecular SN2′ and intramolecular SNV-type cyclization by cleaving dual C–F bonds in a group, which discriminate multiple carbon-nucleophilic sites using single base. Various bicycles bearing monofluorocyclohexene motif were assembled from readily available starting materials under mild conditions via one-pot cascade approach.

Language: Английский

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