Photoinduced copper-catalyzed enantioselective coupling reactions

Chemical Society Reviews, Год журнала: 2023, Номер 52(7), С. 2358 - 2376

Опубликована: Янв. 1, 2023

This review highlights the progress in photoinduced copper-catalyzed enantioselective coupling reactions.

Язык: Английский

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Metal-catalyzed asymmetric reactions enabled by organic peroxides

Chemical Society Reviews, Год журнала: 2024, Номер 53(5), С. 2326 - 2349

Опубликована: Янв. 1, 2024

This review summarizes the advances in metal-catalyzed asymmetric reactions enabled by organic peroxides that have been found to exhibit multifunctionalities, for instance, applied as stoichiometric reactants, reagents, or catalytic amount reagents.

Язык: Английский

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Enantioselective Radical Addition to Ketones through Lewis Acid-Enabled Photoredox Catalysis

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(48), С. 22140 - 22149

Опубликована: Ноя. 22, 2022

Photocatalysis opens up a new window for carbonyl chemistry. Despite multitude of photochemical reactions compounds, visible light-induced catalytic asymmetric transformations remain elusive and pose formidable challenge. Accordingly, the development simple, efficient, economic systems is ideal pursuit chemists. Herein, we report an enantioselective radical photoaddition to ketones through Lewis acid-enabled photoredox catalysis wherein in situ formed chiral N,N'-dioxide/Sc(III)-ketone complex serves as temporary photocatalyst trigger single-electron transfer oxidation silanes generation nucleophilic species, including primary, secondary, tertiary alkyl radicals, giving various enantioenriched aza-heterocycle-based alcohols good excellent yields enantioselectivities. The results electron paramagnetic resonance (EPR) high-resolution mass spectrum (HRMS) measurements provided favorable evidence stereocontrolled addition process involved this reaction.

Язык: Английский

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Emerging Trends in Copper-Promoted Radical-Involved C–O Bond Formations

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(32), С. 17527 - 17550

Опубликована: Авг. 2, 2023

The C–O bond is ubiquitous in biologically active molecules, pharmaceutical agents, and functional materials, thereby making it an important group. Consequently, the development of bond-forming reactions using catalytic strategies has become increasingly research topic organic synthesis because more conventional methods involving strong base acid have many limitations. In contrast to ionic-pathway-based methods, copper-promoted radical-mediated formation experiencing a surge interest owing renaissance free-radical chemistry photoredox catalysis. This Perspective highlights appraises state-of-the-art techniques this burgeoning field. contents are organized according different reaction types working models.

Язык: Английский

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Expanding Reaction Profile of Allyl Carboxylates via 1,2-Radical Migration (RaM): Visible-Light-Induced Phosphine-Catalyzed 1,3-Carbobromination of Allyl Carboxylates

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(15), С. 8275 - 8284

Опубликована: Апрель 5, 2023

Allyl carboxylates are useful synthetic intermediates in a variety of organic transformations, including catalytic nucleophilic/electrophilic allylic substitution reactions and 1,2-difunctionalization reactions. However, the 1,3-difunctionalization allyl remains elusive. Herein, we report first photoinduced, phosphine-catalyzed 1,3-carbobromination carboxylates, affording range valuable substituted isopropyl (sIPC). The transformation has broad functional group tolerance, is amenable to late-stage modification complex molecules gram-scale synthesis, expands reaction profiles phosphine catalysis. Preliminary experimental computational studies suggest non-chain-radical mechanism involving formation an electron donor-acceptor complex, 1,2-radical migration (RaM), Br-atom transfer processes. We anticipate that 1,2-RaM reactivity radical will both serve as platform for development new transformations synthesis.

Язык: Английский

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NIR-II emissive anionic copper nanoclusters with intrinsic photoredox activity in single-electron transfer

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Июнь 1, 2024

Abstract Ultrasmall copper nanoclusters have recently emerged as promising photocatalysts for organic synthesis, owing to their exceptional light absorption ability and large surface areas efficient interactions with substrates. Despite significant advances in cluster-based visible-light photocatalysis, the types of transformations that can catalyze remain limited date. Herein, we report a structurally well-defined anionic Cu 40 nanocluster emits second near-infrared region (NIR-II, 1000−1700 nm) after photoexcitation conduct single-electron transfer fluoroalkyl iodides without need external ligand activation. This photoredox-active efficiently catalyzes three-component radical couplings alkenes, iodides, trimethylsilyl cyanide under blue-LED irradiation at room temperature. A variety fluorine-containing electrophiles nucleophile be added onto an array including styrenes aliphatic olefins. Our current work demonstrates viability using readily accessible metal establish photocatalytic systems high degree practicality reaction complexity.

Язык: Английский

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Photocatalysis Meets Copper Catalysis: A New Opportunity for Asymmetric Multicomponent Radical Cross-Coupling Reactions

Accounts of Chemical Research, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 13, 2024

ConspectusIn recent years, radical-mediated cross-coupling reactions have emerged as a compelling strategy for achieving rich diversity in molecular topologies under benign conditions. However, the inherent high reactivity of radicals presents considerable challenges controlling reaction pathways and selectivity, which often results limited range substrates constrained profile. Given capacity visible-light photoredox catalysis to generate wide variety reactive radical ions controlled manner propensity copper complexes toward species, we envisaged that synergy between chiral catalysts photoactive would pave way developing innovative strategies. This integration is poised unlock broad spectrum enantioselective multicomponent reactions.In this Account, describe our insights efforts realm reactions. These advancements been achieved through application dual photoredox/copper or bifunctional visible light irradiation. Our work systematically divided into two sections based on activation modes. The first section focuses photoinduced copper-catalyzed C-C C-O bond formation addition/nucleophilic trap sequence. discussion particularly concentrated asymmetric carbocyanation carboarylation vinylarenes, 1,3-enynes, 1,3-dienes. findings underscore irradiation with can adeptly modulate pace generation, thus orchestrating consecutive stages ensuring attainment both chemo- stereoselectivity. In domain formation, leveraging carboxylic acids nucleophilic oxygen source, introduce suite esterification benzylic, allylic, propargylic radicals. are derived from precursors, showcasing versatility approach. following highlights discovery field catalysis, enables three-component transformations via direct aromatic alkenes. methodology begins generation formal distonic anions photocatalytic single-electron reduction alkenes, thus, enabling orthogonal reactivity. Employing H

Язык: Английский

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Visible light/copper catalysis enabled Heck-like coupling between alkenes and cyclic sulfonium salts via selective C–S bond cleavage

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(8), С. 2195 - 2200

Опубликована: Янв. 1, 2024

A Heck-like coupling of cyclic sulfonium salts with alkenes via selective C–S bond cleavage using a copper complex as photosensitizer through visible-light-driven redox-neutral process has been developed.

Язык: Английский

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Recent advances in copper-catalyzed multicomponent reactions with photoinduction

Coordination Chemistry Reviews, Год журнала: 2025, Номер 528, С. 216428 - 216428

Опубликована: Янв. 4, 2025

Язык: Английский

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Photoinduced copper-catalyzed asymmetric radical three-component cross-coupling of 1,3-enynes with oxime esters and carboxylic acids

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(11), С. 2773 - 2781

Опубликована: Янв. 1, 2023

A regio- and enantioselective radical three-component coupling of 1,3-enynes, oxime esters, carboxylic acids through photoinduced copper catalysis is reported.

Язык: Английский

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