Metal‐Free Visible‐light Mediated C−S Bond Formation

Asian Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 12(8)

Published: June 26, 2023

Abstract The upsurge in interest the development of methodologies for synthesis sulfur‐containing compounds via use visible‐light has been established as a sustainable tool organic chemistry. Particularly, mediated C−S bond formation gained popularity due to its operational simplicity, minimized by‐products, easy handling, mild reaction conditions, etc. Photochemistry not only provides way synthesize complex molecules but also ability overcome many challenges which are difficult attain by conventional thermal pathways. Owing biological importance compounds, present review focused on under metal‐free conditions visible‐light. objective current is bring out unearthing collection regarding photoredox catalysis. For better understanding, categorized according mode reactions viz , difunctionalization alkenes and alkynes, C−H functionalization, radical cyclization. All each sections described with selected examples proper explanation proposed mechanism.

Language: Английский

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Cr-catalyzed allylic C(sp3)–H addition to aldehydes enabled by photoinduced ligand-to-metal charge transfer

Science China Chemistry, Journal Year: 2024, Volume and Issue: 67(5), P. 1589 - 1595

Published: April 17, 2024

Language: Английский

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Photoinduced Ligand-to-Metal Charge Transfer in Base-Metal Catalysis

Synthesis, Journal Year: 2023, Volume and Issue: 56(13), P. 1967 - 1978

Published: Nov. 21, 2023

Abstract The absorption of light by photosensitizers has been shown to offer novel reactive pathways through electronic excited state intermediates, complementing ground-state mechanisms. Such strategies have applied in both photocatalysis and photoredox catalysis, driven generating intermediates from their long-lived states. One developing area is photoinduced ligand-to-metal charge transfer (LMCT) which coordination a ligand metal center subsequent excitation with results the formation radical reduced center. This mini review concerns foundations recent developments on transition-metal focusing organic transformations made possible this mechanism. 1 Introduction 2 Iron 3 Cobalt 4 Nickel 5 Copper 6 Future Outlook Conclusion

Language: Английский

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Recent advances in catalytic decarboxylative transformations of carboxylic acid groups attached to a non-aromatic sp²or sp carbon

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 21(28), P. 5691 - 5724

Published: Jan. 1, 2023

The current review highlights various decarboxylative transformations of α-keto acids, α,β-unsaturated acids and alkynoic developed since 2017.

Language: Английский

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Visible‐Light Activation of Diorganyl Bis(pyridylimino) Isoindolide Aluminum(III) Complexes and Their Organometallic Radical Reactivity

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(19)

Published: March 21, 2024

Abstract We report on the synthesis and characterization of a series (mostly) air‐stable diorganyl bis(pyridylimino) isoindolide (BPI) aluminum complexes their chemistry upon visible‐light excitation. The redox non‐innocent BPI pincer ligand allows for efficient charge transfer homolytic processes title compounds. This makes them universal platform generation carbon‐centered radicals. photo‐induced cleavage Al−C bonds was investigated by means stationary transient UV/Vis spectroscopy, spin trapping experiments, as well EPR NMR spectroscopy. experimental findings were supported quantum chemical calculations. Reactivity studies enabled utilization reactants in tin‐free Giese‐type reactions carbonyl alkylations under ambient conditions, which both indicated radical‐polar crossover behavior. A deeper understanding physical fundamentals photochemical process provided, furnishing turn new strategy to control reactivity bench‐stable organometallics.

Language: Английский

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Iron-catalyzed decarboxylative radical addition to chiral azomethine imines upon visible light

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(49), P. 6316 - 6319

Published: Jan. 1, 2024

Eco-efficient LMCT based redox-neutral iron-catalyzed decarboxylative radical addition to chiral azomethine imines upon visible light.

Language: Английский

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Light‐Induced Direct Decarboxylative Functionalization of Aromatic Carboxylic Acids

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(21), P. 4263 - 4273

Published: Aug. 28, 2024

Abstract Aryl radicals are important intermediates in organic synthesis. The generation of these reactive species via direct decarboxylation inexpensive and readily available aromatic carboxylic acids is an attractive goal. However, such a process intrinsically exhibits high energy barriers to overcome, which consequence usually require precious metal catalysis, stoichiometric oxidants harsh conditions, suffering from limitations as poor functional group tolerance low atom economy. In recent years, photochemical reactions have provided new approaches address this challenge. Three major strategies been introduced emerging field: 1) one‐pot in‐situ activation benzoic generate benzoyl hypobromites or hypoiodites; 2) the use specialized photocatalysts like biphenyl/1,4‐dicyanobenzene promote through photo‐induced electron transfer charge processes; 3) LMCT (Ligand‐to‐Metal Charge Transfer) strategy where copper iron salts coordinate carboxylate anion upon visible light excitation. On basis three strategies, review will systematically summarize development visible‐light‐induced decarboxylative functionalization acids, focusing on reaction mechanism substrate scope, discuss their prospects

Language: Английский

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Iron‐Catalyzed, Light‐Driven Decarboxylative Oxygenation

European Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 26(44)

Published: Oct. 4, 2023

Abstract An iron‐catalyzed, visible light‐driven, dioxygen mediated decarboxylative oxygenation of carboxylic acids is disclosed. The catalytic system based on naturally existing Mohr salt and simple di(2‐picolyl)amine ligand readily available inexpensive. applicability the method was demonstrated through efficient selective synthesis a range ketones, aldehydes amides including drug derivatives. Based experimental investigations, hypothetical mechanism proposed.

Language: Английский

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Visible-light or sunlight photoredox-catalyzed β-selective acylation of alkenes to access α, β-unsaturated ketones

Organic Chemistry Frontiers, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A general method for accessing α,β-unsaturated ketones through visible-light or sunlight photoredox-catalyzed β-selective acylation of alkenes has been developed.

Language: Английский

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Molecular Design Principles for Photoactive Transition Metal Complexes: A Guide for “Photo-Motivated” Chemists

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: March 27, 2025

Luminescence and photochemistry involve electronically excited states that are inherently unstable therefore spontaneously decay to electronic ground states, in most cases by nonradiative energy release generates heat. This dissipation can occur on a time scale of 100 fs (∼10–13 s) usually needs be slowed down at least the nanosecond (∼10–9 for luminescence intermolecular occur. is challenging task with many different factors consider. An alternative emerging strategy target dissociative lead metal–ligand bond homolysis subnanosecond access synthetically useful radicals. Based thorough review recent advances field, this article aims provide concise guide obtaining luminescent photochemically coordination compounds d-block elements. We hope encourage "photo-motivated" chemists who have been reluctant apply their synthetic other knowledge photophysics photochemistry, we intend stimulate new approaches control state behavior.

Language: Английский

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