Photocatalytic hydrofluoroalkylation of alkenes with carboxylic acids

Nature Chemistry, Journal Year: 2023, Volume and Issue: 15(12), P. 1683 - 1692

Published: Nov. 13, 2023

Language: Английский

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Photoinduced Hydrodifluoromethylation and Hydromethylation of Alkenes Enabled by Ligand-to-Iron Charge Transfer Mediated Decarboxylation

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(3), P. 1300 - 1310

Published: Jan. 11, 2024

Directly utilizing abundant and inexpensive sources of aliphatic carboxylic acids is highly attractive for the synthesis CF2H- CH3-containing compounds. Herein, we report a versatile photoinduced iron-catalyzed platform hydrodifluoromethylation hydromethylation alkenes without need additional stoichiometric oxidants. These two transformations are accomplished by visible-light-induced ligand-to-iron charge transfer open-shell activation system using industrial chemical difluoroacetic acetic as precursors postulated to operate via difluoromethyl methyl radical-mediated decarboxylation mechanism. Experimental results show that strategy also applicable difunctionalization unactivated alkenes. Meanwhile, this provides viable route pharmaceutically active molecules containing deuterated units. The protocol exhibits several features, including mild reaction conditions, divergent radical precursors, operational simplicity scalability, good chemo- regioselectivity, scalability supported continuous flow technology, ability provide high-value building blocks applications in one step.

Language: Английский

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Continuous Flow Decarboxylative Monofluoroalkylation Enabled by Photoredox Catalysis

JACS Au, Journal Year: 2025, Volume and Issue: 5(2), P. 684 - 692

Published: Feb. 2, 2025

Herein, we report a scalable and mild strategy for the monofluoroalkylation of wide array Giese acceptors via visible-light-mediated photoredox catalysis in continuous flow. The use flow technology significantly enhances productivity scalability, whereas mildness conditions functional group tolerance are ensured by leveraging 4CzIPN, transition-metal-free organic photocatalyst. Structurally diverse secondary tertiary monofluoroalkyl radicals can thus be accessed from readily available α-monofluorocarboxylic acids. Given reaction conditions, this protocol is also amenable to late-stage functionalization biologically relevant molecules such as menthol, amantadine, bepotastine, estrone derivatives, rendering it suitable application drug discovery programs, which introduction fluorinated fragments highly sought after. This method was extended enable reductive multicomponent radical-polar crossover transformation rapidly increase complexity assembled architectures single synthetic operation.

Language: Английский

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Iron-mediated ligand-to-metal charge transfer enables 1,2-diazidation of alkenes

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Dec. 23, 2022

Given the widespread significance of vicinal diamine units in organic synthesis, pharmaceuticals and functional materials, as well privileged molecular catalysts, an efficient practical strategy that avoids use stoichiometric strong oxidants is highly desirable. We herein report application ligand-to-metal charge transfer (LMCT) excitation to 1,2-diazidation reactions from alkenes TMSN

Language: Английский

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Photoinduced activation of alkyl chlorides

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(17), P. 6120 - 6138

Published: Jan. 1, 2023

In recent years, the activation of unactivated alkyl chlorides through light-induced processes has emerged as a promising field in radical chemistry, and led to new transformations organic synthesis. Direct utilization C(sp3)-hybridized electrophiles enables facile construction carbon-carbon carbon-heteroatom bonds. Furthermore, studies medicinal chemistry indicate that their presence is associated with high levels success clinical trials. This review summarizes advances photoinduced discusses mechanistic aspects underlying these reactions. We anticipate this will serve valuable resource for researchers chemical bond functionalization, inspire considerable developments drug synthesis, materials science other related disciplines.

Language: Английский

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Regiodivergent electroreductive defluorinative carboxylation ofgem-difluorocyclopropanes

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(8), P. 3095 - 3102

Published: Jan. 1, 2023

A regiodivergent electrochemical defluorocarboxylation of gem -difluorocyclopropanes is realized, providing access to branched and linear carboxylated monofluorinated alkenes.

Language: Английский

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Visible light-initiated manganese-catalyzed hydrosulfonylation of alkenes

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(10), P. 4122 - 4128

Published: Jan. 1, 2023

A visible light-initiated manganese-catalyzed radical hydrosulfonylation of a wide range structurally diverse alkenes using commercially available and relatively cheap sulfonyl chlorides as sources is described.

Language: Английский

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Silver-Promoted Three-Component Synthesis of Perfluoroalkenyl Pyrroles through Partial Defluorinative Functionalization of Perfluoroalkyl Halides

Organic Letters, Journal Year: 2024, Volume and Issue: 26(29), P. 6197 - 6202

Published: July 15, 2024

A silver-promoted three-component heterocyclization of alkynes, perfluoroalkyl halides, and 1,3-dinucleophiles was developed for the efficient synthesis privileged (E)-perfluoroalkenyl pyrroles. The reaction proceeded through a rationally designed sequence radical perfluoroalkylation intramolecular defluorinative [3 + 2]-heterocyclization. utility halide as perfluoroalkenyl reagent, by selective controllable functionalization two inert C(sp3)–F bonds at vicinal carbon centers on chain, provides new mode value-added organofluorides starting from easily available low-cost fluorinated feedstock.

Language: Английский

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Photoinduced Three-Component Carboarylation of Unactivated Alkenes with Protic C(sp³)–H Feedstocks

Organic Letters, Journal Year: 2022, Volume and Issue: 24(41), P. 7677 - 7684

Published: Oct. 10, 2022

A general and mild strategy involving three-component carboarylation of unactivated alkenes with protic C(sp3)–H feedstocks via photoredox catalysis was reported. This catalytic system is compatible a broad range alkenes, cyano-substituted arenes, diverse feedstocks. The synthetic value this protocol demonstrated by the late-stage functionalization complex molecules synthesis antiallergies including pheniramine, chlorpheniramine, brompheniramine.

Language: Английский

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Intermolecular Redox-Neutral Carboamination of C–C Multiple Bonds Initiated by Transition-Metal-Catalyzed C–H Activation

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(23), P. 14754 - 14772

Published: Nov. 18, 2022

Carboamination of readily available feedstock-like alkenes, alkynes, and allenes has proven to be an efficient powerful tool for the synthesis diverse valuable amine derivatives relevance medicinal chemistry, biochemistry, material science. Among these developed carboamination methodologies, direct use C–H activation strategy leverage process is particularly attractive due ubiquity such bonds in organic molecules. In this review, we provide overview development intermolecular across C–C π-bonds initiated by a redox-neutral nonannulative manner, with emphasis on synthetic mechanistic aspects. principle, review summarized reactions key feature involving initial metalation followed migratory insertion into terminated electrophilic amination quenching, thus, it ordered sources C- N-based functionalities further divided π-compounds.

Language: Английский

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