General Defluoroalkylation of Trifluoromethylarenes with Both Electron-Donating and -Withdrawing Alkenes

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(17), P. 12591 - 12609

Published: Aug. 14, 2024

The incorporation of gem-difluoromethylene units into organic molecules remains a formidable challenge. Conventional methodologies for constructing aryldifluoromethyl derivatives relied on the use high-functional fluorinating regents under harsh conditions. Herein, we report general and efficient photoredox catalytic systems defluoroalkylation readily available trifluoromethylarenes through selective C–F cleavage to deliver gem-difluoromethyl radicals which proceed reductive addition both electron-donating withdrawing alkenes transition-metal free Mechanistic studies reveal that thiol serves as photocatalyst HAT reagent visible light irradiation. This synergistic photocatalysis catalysis protocol exhibits ample salient features such high chemo- regioselectivity, broad substrate scope, amenable gram-scale synthesis late-stage modification bioactive molecules.

Language: Английский

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Photoreduction of Trifluoromethyl Group: Lithium Ion Assisted Fluoride‐Coupled Electron Transfer from EDA Complex

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(33)

Published: April 11, 2024

Photoinduced single-electron reduction is an efficient method for the mono-selective activation of C-F bond on a trifluoromethyl group to construct difluoroalkyl group. We have developed electron-donor-acceptor (EDA) complex mediated transfer (EDA-SET) α,α,α-trifluoromethyl arenes in presence lithium salt give α,α-difluoroalkylarenes. The was realized by iodide and triethylamine, two common feedstock reagents. Mechanistic studies revealed generation α,α-difluoromethyl radical defluorination, followed addition alkenes. Lithium interacted with fluorine atom promote photoinduced EDA complex. Computational indicated that lithium-assisted defluorination occurred concertedly. call this phenomenon fluoride-coupled electron (FCET). FCET novel approach synthesis organofluorine compounds.

Language: Английский

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Visible-Light Excited Copper Activating Unactivated Alkyl Iodides for Radical Addition/Cyclization to Access Oxindole Derivatives

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

The photocopper catalyst facilitates halogen atom transfer to give unactivated alkyl radicals, which is critical for achieving radical cyclization in the absence of an exogenous photocatalyst.

Language: Английский

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Recent Discovery, Development, and Synthetic Applications of Formic Acid Salts in Photochemistry

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 136(4)

Published: Oct. 9, 2023

Abstract The advancement of sustainable photoredox catalysis in synthetic organic chemistry has evolved immensely because the development versatile and cost‐effective reagents. In recent years, a substantial effort been dedicated to exploring utility formic acid salts various photochemical reactions. this context, formates have demonstrated diverse capabilities, functioning as reductants, sources carbonyl groups, reagents for hydrogen atom transfer. Notably, CO 2 ⋅ – radical anion derived from formate exhibits strong reductant properties cleaving both C−X C−O bonds. Moreover, these play pivotal role carboxylation reactions, further highlighting their significance variety transformations. ability serve sources, transfer reveal exciting possibilities chemistry. This minireview highlights an array captivating discoveries, underscoring crucial distinctive methods, enabling access wide range value‐added compounds.

Language: Английский

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Chemoselective Hydroheteroarylation of Alkenes via Photoredox-Neutral Proton- and BF₃-Mediated Electron Transfer

Organic Letters, Journal Year: 2024, Volume and Issue: 26(36), P. 7707 - 7712

Published: Aug. 28, 2024

Herein, we have developed a complementary entry to enable hydroheteroarylation of alkenes involving basically photoredox dearomatizative heterocyclic carbon radical formation through acid-coupled electron transfer followed by Giese addition. While protonic solvent and thiophenol additive enabled two molecular hydroheteroarylations alkenes, the nonproton environment with BF

Language: Английский

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