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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Photoredox/Copper Cooperatively Catalyzed Arylalkynylation of [1.1.1]Propellane

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

Published: March 20, 2025

We present a sp2–sp3/sp3–sp bond formation reaction through three-component coupling strategy involving terminal alkynes, [1.1.1]propellane, and aryl thianthrenium salts that are prepared from arenes. The employs dual photo/copper catalysis system provides streamlined approach for assembling 1-alkynyl-3-aryl bicyclo[1.1.1]pentane derivatives with broad spectrum of functional group compatibility. Mechanistic studies suggest the generation radicals copper alkynide intermediates was involved.

Language: Английский

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Copper-Catalyzed Diastereoselective Addition of a [1,1,1]Propellane Dimer to N-tert-Butanesulfinyl Aldimines

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

Published: March 21, 2025

[1,1,1]Propellane is typically used as a building block for the construction of bicyclo[1,1,1]pentanes and cyclobutanes. In this work, diverse chiral bi(methylenecyclobutylidene) complexes were synthesized by diastereoselective addition [1,1,1]propellane dimer to N-tert-butanesulfinyl aldimines in presence copper bipyridine. Density functional theory calculations revealed that both step regeneration catalyst contributed generation favored (Ss,S,S)-diastereomer.

Language: Английский

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Photocatalytic Difunctionalization of [1.1.1]Propellane

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

Published: March 27, 2025

The hunt for new molecular structures to improve the efficacy of biologically active molecules is at forefront pharmaceutical chemistry. So synthetic chemists have always been busy in last few decades synthesizing and testing frameworks which would work as more efficient bioisosteres present bioactive functional groups. In this area, bicyclo[1.1.1]pentane (BCP) framework has identified a promising candidate. It being utilized bioisostere aryl, tert-butyl, alkynes, etc. Now major precursor various BCP derivatives [1.1.1]propellane functionalization drawn widespread attention organic chemist community. Over past two decades, use visible light synthesis rapidly gained popularity, it represents one most approaches aligned with principles green sustainable chemistry, several interesting papers covering photocatalytic difunctionalization also published decade. This particular field really attracted That why we decided compile review article articles related under conditions. Here review, categorized discussed three categories, namely i) without using any catalyst, ii) organocatalysts, iii) metal catalysts deeper understanding key aspects these transformations.

Language: Английский

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Photoredox/Palladium-Catalyzed Reduction Alkylation of Imines and Ammonium Salts via Dual C–N Bond Cleavage

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 16, 2025

Here, we report a photoredox/palladium-catalyzed reduction alkylation of imines and ammonium salts via dual C-N cleavage. This reaction proceeds under mild, green, operationally simple conditions, offering broad scope secondary amine compounds with alpha quaternary carbon. Mechanistic studies indicate that the α-amino carbanion, generated by successive single-electron transfer process, is key intermediate in photoredox/palladium catalysis.

Language: Английский

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