Iron Photoredox Catalysis–Past, Present, and Future

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(17), P. 9369 - 9388

Published: April 20, 2023

Photoredox catalysis of organic reactions driven by iron has attracted substantial attention throughout recent years, due to potential environmental and economic benefits. In this Perspective, three major strategies were identified that have been employed date achieve reactivities comparable the successful noble metal photoredox catalysis: (1) Direct replacement a center in archetypal polypyridyl complexes, resulting metal-centered photofunctional state. (2) situ generation photoactive complexes substrate coordination where are via intramolecular electron transfer involving charge-transfer states, for example, through visible-light-induced homolysis. (3) Improving excited-state lifetimes redox potentials states new ligand design. We seek give an overview evaluation developments rapidly growing field and, at same time, provide outlook on future iron-based catalysis.

Language: Английский

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Merging Photoinduced Iron-Catalyzed Decarboxylation with Copper Catalysis for C–N and C–C Couplings

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(3), P. 1678 - 1685

Published: Jan. 13, 2023

We report a photoinduced iron/copper dual-catalytic strategy for the radical decarboxylation functionalization of aliphatic carboxylic acids. The ligand-to-iron charge transfer process under light was initially occurred to generate an unstabilized alkyl radical, and copper catalyst delivered enabled subsequent coupling reactions form C–N or C–C bonds. By merging iron-catalyzed with catalysis, this system allows smooth conversion wide range acids amination, decarboxylative dehydrogenation, alkylation efficiently. A variety complex drug natural molecules is applicable, suggesting that would facilitate rapid compound library synthesis benefit discovery pharmaceutical agents.

Language: Английский

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Decarboxylative sulfoximination of benzoic acids enabled by photoinduced ligand-to-copper charge transfer

Chemical Science, Journal Year: 2022, Volume and Issue: 13(45), P. 13611 - 13616

Published: Jan. 1, 2022

Sulfoximines are synthetically important scaffolds and serve roles in drug discovery. Currently, there is no solution to decarboxylative sulfoximination of benzoic acids; although thoroughly investigated, limited substrate scope harsh reaction conditions still hold back traditional thermal aromatic functionalization. Herein, we realize the first acids via photo-induced ligand copper charge transfer (copper-LMCT)-enabled carbometalation. The transformation proceeds under mild conditions, has a broad scope, can be applied late-stage functionalization complex small molecules.

Language: Английский

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The great strides of iron photosensitizers for contemporary organic photoredox catalysis: On our way to the holy grail?

Coordination Chemistry Reviews, Journal Year: 2023, Volume and Issue: 500, P. 215522 - 215522

Published: Nov. 9, 2023

Language: Английский

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Decarboxylative Sulfonylation of Carboxylic Acids under Mild Photomediated Iron Catalysis

Organic Letters, Journal Year: 2024, Volume and Issue: 26(12), P. 2381 - 2386

Published: March 15, 2024

Organic sulfones are an important class of chemical compounds widely used in many research fields. The direct decarboxylative sulfonylation carboxylic acids is attractive but challenging, particularly when iron as a metal catalyst. Herein, we describe photoinduced iron-catalytic method for the synthesis directly using via radical-based decarboxylation. This protocol mild, highly efficient, and easy-to-operate. A broad scope carbon electrophiles could be well tolerated. mechanism involving iron-catalyzed decarboxylation, radical transfer, single-electron reduction, nucleophilic attack proposed.

Language: Английский

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Unleashing the potentiality of metals: synergistic catalysis with light and electricity

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(14), P. 4024 - 4040

Published: Jan. 1, 2024

This review provides a comprehensive overview of metal catalysis in photo-electrochemical systems, discussing reaction mechanisms and offering prospects for this triadic catalytic mode.

Language: Английский

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Photoinduced C−O Bond Formation through C−C Bond Cleavage of Alcohols by Suppressing Alcohol Oxidation

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(7), P. 1595 - 1605

Published: Feb. 3, 2024

Abstract Herein, we present a photoinduced deconstructive alkoxyamination of alkyl alcohols catalyzed by iron salts. This transformation involves the initiation alkoxy radicals through chlorine radical‐induced radical formation, followed β ‐scission and trapping resulting carbon with 2,2,6,6‐tetramethylpiperidin‐1‐yl (TEMPO). reaction exhibits broad substrate scope (40 examples), including primary secondary that are prone to oxidation combination TEMPO iron. Mechanistic investigations have revealed enhanced coordination chloride ion center inhibits OH process, thereby enabling tolerance alcohols.

Language: Английский

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Synergistic use of photocatalysis and convergent paired electrolysis for nickel-catalyzed arylation of cyclic alcohols

Science Bulletin, Journal Year: 2024, Volume and Issue: 69(12), P. 1866 - 1874

Published: April 16, 2024

Language: Английский

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Deconstructive Cyanomethylation Enabled by Radical Cross‐Coupling through Multiple C−C Bond and C−H Bond Cleavage

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(7), P. 1072 - 1081

Published: March 17, 2023

Abstract Being in its infancy, radical cross‐coupling is highly efficient for C−C bond construction, though suffers from selectivity problems and limited reaction types. New methodologies to realize selectively are desired. Herein, an iron catalyzed deconstructive cyanomethylation of unstrained cyclic linear alcohols with acetonitrile has been developed through cross‐coupling. The unprecedented method enables a ring‐opening functionalization cyclohexanols produce α‐cyanomethyl ketones. Notably, the challenging involves twice single cleavage β‐scission alkoxyl intermediates, C( sp 3 )−H transformation via hydrogen atom transfer (HAT) procedures, resulting two carbon species that process form new )−C( ) selectively. α‐arylketo α‐aryl substituted tertiary can also be applied as substrates, leading terminal cyano‐functionalized products, ketone leaving fragment. Mechanistically, procedure generate chlorine in‐situ formed intermediate cycloalkyl hypochlorite was suggested. magnified image

Language: Английский

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Recent Development of Photoinduced Iron-Catalysis in Organic Synthesis

Chinese Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 43(4), P. 1386 - 1386

Published: Jan. 1, 2023

In recent years, the development and application of transition metal ruthenium or iridium complexes based photocatalysts have opened up a new research field for organic synthesis, which provides mild efficient strategies construction chemical bonds transformations.In order to enrich types photocatalysts, broaden scope photocatalysis, develop green sustainable chemistry, some low-cost easily available organometallic with copper iron were applied as recently.Iron-complexes feature non-toxicity, rich variety, unique property charge transfer from ligands metals, enable them show extraordinary capability in photocatalytic synthesis.According different reaction types, this review focuses on photoinduced iron-catalysis synthesis including C-H bond functionalization, C-C bifunctionalization alkenes, cross-coupling reaction, decarboxylative selective oxidation reduction.

Language: Английский

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