Decarboxylative cross-nucleophile coupling via ligand-to-metal charge transfer photoexcitation of Cu(ii) carboxylates

Nature Chemistry, Journal Year: 2022, Volume and Issue: 14(1), P. 94 - 99

Published: Jan. 1, 2022

Language: Английский

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Photoelectrochemical Asymmetric Catalysis Enables Direct and Enantioselective Decarboxylative Cyanation

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(44), P. 20201 - 20206

Published: Oct. 31, 2022

The development of efficient and sustainable methods for decarboxylative transformations is great importance due to the ease availability nontoxicity carboxylic acids. Despite tremendous efforts in this area, it remains challenging develop enantioselective direct from Herein we disclose a photoelectrocatalytic method cyanation. photoelectrochemical reactions convert acids enantioenriched nitriles by employing cerium/copper relay catalysis with cerium salt catalytic decarboxylation chiral copper complex stereoselective C-CN formation.

Language: Английский

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Free Carboxylic Acids: The Trend of Radical Decarboxylative Functionalization

European Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 26(21)

Published: April 7, 2023

Abstract The exceptional versatility of carboxylic acids has been extensively exploited in organic synthesis across several decades. There a recent upsurge radical decarboxylative transformations. process can be initiated under mild conditions, and the resultant radicals have orthogonal reactivities to closed‐shell species, thus providing immense opportunities for streamlining novel reactions. use free is most desirable owing its high atom step economy. Aiming demonstrate attractiveness strategy inspire chemists tackle existing challenges, this review outlines advances on functionalization acids.

Language: Английский

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Photoinduced Hydrodifluoromethylation and Hydromethylation of Alkenes Enabled by Ligand-to-Iron Charge Transfer Mediated Decarboxylation

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(3), P. 1300 - 1310

Published: Jan. 11, 2024

Directly utilizing abundant and inexpensive sources of aliphatic carboxylic acids is highly attractive for the synthesis CF2H- CH3-containing compounds. Herein, we report a versatile photoinduced iron-catalyzed platform hydrodifluoromethylation hydromethylation alkenes without need additional stoichiometric oxidants. These two transformations are accomplished by visible-light-induced ligand-to-iron charge transfer open-shell activation system using industrial chemical difluoroacetic acetic as precursors postulated to operate via difluoromethyl methyl radical-mediated decarboxylation mechanism. Experimental results show that strategy also applicable difunctionalization unactivated alkenes. Meanwhile, this provides viable route pharmaceutically active molecules containing deuterated units. The protocol exhibits several features, including mild reaction conditions, divergent radical precursors, operational simplicity scalability, good chemo- regioselectivity, scalability supported continuous flow technology, ability provide high-value building blocks applications in one step.

Language: Английский

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Photoinduced Ligand‐to‐Metal Charge Transfer of Carboxylates: Decarboxylative Functionalizations, Lactonizations, and Rearrangements

Advanced Synthesis & Catalysis, Journal Year: 2022, Volume and Issue: 364(24), P. 4189 - 4230

Published: Dec. 3, 2022

Abstract In the quest for sustainable processes, selection of resources and catalysts is central importance. Carboxylic acids, which are abundant, stable ideally biobased feedstocks, can be considered as attractive platforms towards a range functionalized molecules. A recent resurgence photoinduced ligand‐to‐metal charge transfer (LMCT) carboxylates led to tremendous developments in field earth‐abundant metal mediated, visible‐light induced (non)‐decarboxylative transformations carboxylic acids. These reactions combine use available starting materials, low‐consuming energy source abundant catalysts. Besides these undeniable advantages, they also provide mild, highly selective innovative conditions complex molecule functionalization. The objective this review give an overview advances LMCT with special focus on mechanistic aspects transformations. magnified image

Language: Английский

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Exploiting photoredox catalysis for carbohydrate modification through C–H and C–C bond activation

Nature Reviews Chemistry, Journal Year: 2022, Volume and Issue: 6(11), P. 782 - 805

Published: Sept. 21, 2022

Language: Английский

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Electrophotochemical Decarboxylative Azidation of Aliphatic Carboxylic Acids

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(17), P. 10661 - 10667

Published: Aug. 16, 2022

We report an electrophotochemical metal-catalyzed strategy that harnesses the power of light and electricity for radical decarboxylative functionalization aliphatic carboxylic acids. This environmentally friendly protocol smoothly converts a diverse array acids into corresponding alkyl azides without using chemical oxidants or azido-group transfer reagents. The visible energy electric can be applied in spatially separated fashion with modular electro-flow-cell large-scale synthesis.

Language: Английский

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Electrophotochemical Metal‐Catalyzed Enantioselective Decarboxylative Cyanation

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(24)

Published: Jan. 13, 2023

Abstract In contrast to the rapid growth of electrophotocatalysis in recent years, enantioselective catalytic reactions powered by this unique methodology remain rare. work, we report an electrophotochemical metal‐catalyzed protocol for direct asymmetric decarboxylative cyanation aliphatic carboxylic acids. The synergistic merging cerium catalysis and electrochemical copper permits mild reaction conditions formation utilization key carbon centered radicals combining power light electrical energy. Electrophotochemical enables radical decarboxylation produce alkyl radicals, which could be effectively intercepted construction C−CN bonds a highly stereoselective fashion. This environmentally benign method smoothly converts diverse array arylacetic acids into corresponding nitriles good yields enantioselectivities without using chemical oxidants or pre‐functionalization acid substrates can readily scaled up.

Language: Английский

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Redox-neutral carbon–heteroatom bond formation under photoredox catalysis

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(46), P. 7004 - 7027

Published: Jan. 1, 2023

This feature article presents all the recent reports on photoredox-catalyzed redox-neutral carbon–heteroatom coupling reactions up to March 2023.

Language: Английский

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Photoredox‐Catalyzed Decarboxylative Bromination, Chlorination and Thiocyanation Using Inorganic Salts

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(38)

Published: July 31, 2023

Abstract Decarboxylative halogenation reactions of alkyl carboxylic acids are highly valuable for the synthesis structurally diverse halides. However, many reported protocols rely on stoichiometric strong oxidants or electrophilic halogenating agents. Herein, we describe visible‐light photoredox‐catalyzed decarboxylative N ‐hydroxyphthalimide‐activated that avoid and use inexpensive inorganic halide salts as Bromination with lithium bromide proceeds under simple, transition‐metal‐free conditions using an organic photoredox catalyst no other additives, whereas dual photoredox‐copper catalysis is required chlorination chloride. The mild display excellent functional‐group tolerance, which demonstrated through transformation a range complex acid containing natural products into corresponding bromides chlorides. In addition, show generality photoredox‐copper‐catalyzed functionalization by extension to thiocyanation potassium thiocyanide, was applied thiocyanates.

Language: Английский

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