Photons or Electrons? A Critical Comparison of Electrochemistry and Photoredox Catalysis for Organic Synthesis

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 2487 - 2649

Published: Nov. 9, 2021

Redox processes are at the heart of synthetic methods that rely on either electrochemistry or photoredox catalysis, but how do and catalysis compare? Both approaches provide access to high energy intermediates (e.g., radicals) enable bond formations not constrained by rules ionic 2 electron (e) mechanisms. Instead, they 1e mechanisms capable bypassing electronic steric limitations protecting group requirements, thus enabling chemists disconnect molecules in new different ways. However, while providing similar intermediates, differ several physical chemistry principles. Understanding those differences can be key designing transformations forging disconnections. This review aims highlight these similarities between comparing their underlying principles describing impact electrochemical photochemical methods.

Language: Английский

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Sequential and direct multicomponent reaction (MCR)-based dearomatization strategies

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(23), P. 8721 - 8748

Published: Jan. 1, 2020

This review focuses on the comprehensive understanding of different multicomponent reaction (MCR) cascades involving dearomatization as characteristic step.

Language: Английский

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P-chirogenic phosphorus compounds by stereoselective Pd-catalysed arylation of phosphoramidites

Nature Catalysis, Journal Year: 2021, Volume and Issue: 5(1), P. 10 - 19

Published: Dec. 23, 2021

Language: Английский

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Mn-Catalyzed Electrooxidative Undirected C–H/P–H Cross-Coupling between Aromatics and Diphenyl Phosphine Oxides

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(7), P. 4295 - 4300

Published: March 23, 2021

C–P bonds are widely found in a great many bioactive compounds and functional molecules. Transition-metal-catalyzed dehydrogenative C–H/P–H cross-coupling plays crucial part bond formation since it requires no pretreatment of substrates. Herein, we reported Mn-catalyzed electrochemical intermolecular between aryl C–H diphenyl phosphine oxides. In undivided cells, series phosphorylation or diphosphorylation products could be obtained separately by adjusting the proportion A catalytic amount inexpensive Mn(II) salt was used, external chemical oxidants were needed this process. kinetic isotope effect experiment suggested that activation not rate-determining step.

Language: Английский

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Cobaloxime Photocatalysis for the Synthesis of Phosphorylated Heteroaromatics

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(40)

Published: Aug. 1, 2022

Abstract Herein, cobaloxime is used for the first time as a catalyst synthesis of phosphorylated heteroaromatics, which an intriguing and versatile functional motif. With visible‐light irradiation, not only oxidizes phosphine oxides to form phosphorus radicals (P‐radicals) subsequent reaction with radical acceptor isocyanides or but also combines intermediate β ‐H elimination, thereby producing heteroaromatics H 2 CH 4 byproduct. Phosphine dialkyl, alkylaryl, diaryl substituents could be directly transformed into phenanthridines, benzothiazoles, isoquinolines, common heteroaromatics. This catalytic system features extremely mild conditions, broad substrate scope good excellent yields. Scale‐up sunlight show great application potential in green important organophosphorus chemicals.

Language: Английский

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Synthesis of P-stereogenic cyclicphosphinic amidesviaelectrochemically enabled cobalt-catalyzed enantioselective C–H annulation

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(9), P. 3606 - 3614

Published: Jan. 1, 2023

We describe a cobalta-electro-catalyzed enantioselective C–H annulation of arylphosphinamides with alkynes for P-stereogenic compounds via desymmetrization and kinetic resolution processes.

Language: Английский

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Convergent Deboronative and Decarboxylative Phosphonylation Enabled by the Phosphite Radical Trap “BecaP”

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(33), P. 18649 - 18657

Published: Aug. 8, 2023

Carbon-phosphorus bond formation is significant in synthetic chemistry because phosphorus-containing compounds offer numerous indispensable biochemical roles. While there a plethora of methods to access organophosphorus compounds, phosphonylations readily accessible alkyl radicals form aliphatic phosphonates are rare and not commonly used synthesis. Herein, we introduce novel phosphorus radical trap "BecaP" that enables facile efficient phosphonylation under visible light photocatalytic conditions. Importantly, the ambiphilic nature BecaP allows redox neutral reactions with both nucleophilic (activated by single-electron oxidation) electrophilic reduction) precursors. Thus, broad scope feedstock potassium trifluoroborate salts active carboxylate esters could be employed, each class substrate proceeding through distinct mechanistic pathway. The mild conditions applicable late-stage installation phosphonate motifs into medicinal agents natural products, which showcased straightforward conversion baclofen (muscle relaxant) phaclofen (GABAB antagonist).

Language: Английский

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A H4SiW12O40-catalyzed three-component tandem reaction for the synthesis of 3,3-disubstituted isoindolinones

Chinese Chemical Letters, Journal Year: 2023, Volume and Issue: 35(1), P. 108480 - 108480

Published: April 20, 2023

Language: Английский

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Synthetic Methods for Azaheterocyclic Phosphonates and Their Biological Activity: An Update 2004–2024

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(12), P. 7907 - 7975

Published: May 29, 2024

The increasing importance of azaheterocyclic phosphonates in the agrochemical, synthetic, and medicinal field has provoked an intense search development synthetic routes for obtaining novel members this family compounds. This updated review covers methodologies established since 2004, focusing on synthesis phosphonates, which phosphonate moiety is directly substituted onto to structure. Emphasizing recent advances, classifies newly developed approaches according ring size providing information biological activities whenever available. Furthermore, summarizes various methods formation C–P bonds, examining sustainable such as Michaelis–Arbuzov reaction, Michaelis–Becker Pudovik Hirao coupling, Kabachnik–Fields reaction. After analyzing applications investigated years, a predominant focus evaluation these compounds anticancer agents evident. emerging underline versatility potential compounds, highlighting need continued research expand interesting family.

Language: Английский

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Phototriggered Self-Catalyzed Phosphorylation of 3,4-Dihydroquinoxalin-2(1H)-ones with Diarylphosphine Oxides in EtOH

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 19, 2024

A highly effective external photocatalyst- and additive-free method for the phosphorylation of 3,4-dihydroquinoxalin-2(1

Language: Английский

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