Photo‐/Electrocatalytic Difunctionalization of Alkenes Enabled by C‐H Radical Functionalization

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(62)

Published: Aug. 10, 2024

The difunctionalization of alkenes represents a powerful tool to incorporate two functional groups into the alkene bones for increasing molecular complexity and has been widely utilizations in chemical synthesis. Upon catalysis green, sustainable, mild photo-/electrochemistry technologies, much attentions have attracted development new tactics transformations important alkane feedstocks driven by C-H radical functionalization. Herein, we summarize recent advances photo-/electrocatalytic enabled We detailedly discuss substrate scope mechanisms reactions selecting impressive synthetic examples, which are divided four sections based on final terminated step, including oxidative radical-polar crossover coupling, reductive radical-radical transition-metal-catalyzed coupling.

Language: Английский

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Recent Advances in Carbon-Centered Radical-Initiated Olefin Transformation Chemistry

Catalysts, Journal Year: 2025, Volume and Issue: 15(5), P. 461 - 461

Published: May 8, 2025

In recent years, carbon-centered radical-initiated olefin transformation reactions, including alkene Heck-type alkylation, hydroalkylation, and difunctionalization have attracted increasing attention been extensively developed. This review summarizes the advances in chemistry, such as radical-mediated reactions. area of research is divided into several sections based on types reactions divergent formation processes radicals. Drawing our group’s investigations, we show that efficient strategies gained significant traction synthetic chemistry due to their ability rapidly install functional groups enhance molecular complexity.

Language: Английский

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Visible‐Light‐Mediated Activation of Remote C(sp3)‐H Bonds by Carbon‐Centered Biradical via Intramolecular 1,5‐ or 1,6‐Hydrogen Atom Transfer

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(38)

Published: June 21, 2024

In this study, we introduce a novel intramolecular hydrogen atom transfer (HAT) reaction that efficiently yields azetidine, oxetane, and indoline derivatives through mechanism resembling the carbon analogue of Norrish-Yang reaction. This process is facilitated by excited triplet-state carbon-centered biradicals, enabling 1,5-HAT suppressing critical 1,4-biradical intermediates from undergoing Norrish Type II cleavage reaction, pioneering unprecedented 1,6-HAT reactions initiated alkenes. We demonstrate synthetic utility compatibility method across various functional groups, validated scope evaluation, large-scale synthesis, derivatization. Our findings are supported control experiments, deuterium labeling, kinetic studies, cyclic voltammetry, Stern-Volmer density theory (DFT) calculations.

Language: Английский

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TMSCN-Promoted Difunctionalization of Alkenes for the Synthesis of Alcohol Derivatives

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(17), P. 12062 - 12070

Published: Aug. 15, 2024

A TMSCN-promoted difunctionalization of styrenes with CHCl3 and TBHP is reported via the radical addition/cross coupling process. wide range dichloromethyl-substituted alcohol derivatives were synthesized under transition-metal-free conditions. Besides, this method also applicable to unactive alkenes. The key success lies in role TMSCN, which prevents reaction toward dichloromethylperoxylation olefins. This represents an alternative approach for synthesizing diverse using readily available substrates, holding significant promise fields pharmaceutical chemistry natural product synthesis.

Language: Английский

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Visible‐Light‐Mediated Activation of Remote C(sp³)−H Bonds by Carbon‐Centered Biradical via Intramolecular 1,5‐ or 1,6‐Hydrogen Atom Transfer

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(38)

Published: June 21, 2024

Abstract In this study, we introduce a novel intramolecular hydrogen atom transfer (HAT) reaction that efficiently yields azetidine, oxetane, and indoline derivatives through mechanism resembling the carbon analogue of Norrish‐Yang reaction. This process is facilitated by excited triplet‐state carbon‐centered biradicals, enabling 1,5‐HAT suppressing critical 1,4‐biradical intermediates from undergoing Norrish Type II cleavage reaction, pioneering unprecedented 1,6‐HAT reactions initiated alkenes. We demonstrate synthetic utility compatibility method across various functional groups, validated scope evaluation, large‐scale synthesis, derivatization. Our findings are supported control experiments, deuterium labeling, kinetic studies, cyclic voltammetry, Stern–Volmer density theory (DFT) calculations.

Language: Английский

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