Ligand‐to‐Metal Charge Transfer (LMCT) Photochemistry at 3d‐Metal Complexes: An Emerging Tool for Sustainable Organic Synthesis

ChemCatChem, Год журнала: 2022, Номер 14(19)

Опубликована: Авг. 11, 2022

Abstract Despite the rich photochemistry of 3d‐metal complexes, utilization excited‐state reactivity these compounds in organic synthesis has been historically overlooked. The advent photoredox catalysis changed perception synthetic chemists towards photochemistry, and nowadays potential photoinduced, outer‐sphere single‐electron transfer events is widely recognized. More recently, an emerging new mode photoactivation taken spotlight, based on inner‐sphere triggered by population ligand‐to‐metal charge‐transfer (LMCT) excited states. Contrarily to photoredox, LMCT‐activation does not rely matching redox potentials, offers unique profiles particularly well suited Earth‐abundant metal complexes. Those appealing features are propelling development methods using this blueprint generate highly reactive open‐shell species under mild conditions. aim contribution provide a didactical tool for comprehension concept facilitate methodologies achieve sustainable chemical transformations.

Язык: Английский

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Iron Photoredox Catalysis–Past, Present, and Future

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(17), С. 9369 - 9388

Опубликована: Апрель 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.

Язык: Английский

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Photoinduced Ligand-to-Metal Charge Transfer (LMCT) of Fe Alkoxide Enabled C–C Bond Cleavage and Amination of Unstrained Cyclic Alcohols

Organic Letters, Год журнала: 2022, Номер 24(3), С. 977 - 982

Опубликована: Янв. 14, 2022

We report an alkoxy radical process for the C-C bond cleavage and functionalization of unstrained tertiary secondary cyclic alcohols. In absence a chlorine atom, readily available iron catalysts [Fe(OBu-t)3 or Fe(acac)3/t-BuONa] facilitate formation via direct ligand-to-metal charge transfer Fe alkoxide further enable ring opening amination The remote amino carbonyl compounds could be obtained with broad scope in up to excellent yields under mildly redox-neutral system. Light-driven electron transfer, formation, subsequent β-scission were keys transformation.

Язык: Английский

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

ACS Catalysis, Год журнала: 2023, Номер 13(3), С. 1678 - 1685

Опубликована: Янв. 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.

Язык: Английский

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Recent advances in FeCl3-photocatalyzed organic reactions via hydrogen-atom transfer

Chinese Chemical Letters, Год журнала: 2024, Номер 35(9), С. 109517 - 109517

Опубликована: Янв. 21, 2024

Язык: Английский

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Radical Brook rearrangement: past, present, and future

Chemical Society Reviews, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

This review aims to provide an overview of radical Brook rearrangement, which is organized by grouping three type reactive species generated via the unique rearrangement process.

Язык: Английский

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Visible-Light-Induced Decarboxylative Fluorination of Aliphatic Carboxylic Acids Catalyzed by Iron

Organic Letters, Год журнала: 2022, Номер 24(32), С. 5972 - 5976

Опубликована: Авг. 11, 2022

An efficient and inexpensive protocol for the direct decarboxylative fluorination of aliphatic carboxylic acids catalyzed with iron salts under visible light is presented. This new method allows facile a diverse array even on gram scale using Schlenk flask without loss efficiency. Mechanistic studies suggest that photoinduced ligand-to-metal charge transfer process enables generation key step to generate carboxyl radical intermediates.

Язык: Английский

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

Advanced Synthesis & Catalysis, Год журнала: 2022, Номер 364(24), С. 4189 - 4230

Опубликована: Дек. 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

Язык: Английский

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Photoredox/Cobalt Dual Catalysis Enabled Regiospecific Synthesis of Distally Unsaturated Ketones with Hydrogen Evolution

ACS Catalysis, Год журнала: 2022, Номер 12(6), С. 3710 - 3718

Опубликована: Март 9, 2022

In this report, we present a photoredox/cobalt dual catalytic system for the synthesis of distally unsaturated ketones. Upon cooperative utilization an organo photoredox catalyst and cobaloxime catalyst, sequential ring-opening C–C bond scission dehydrogenation nonstrained tertiary cycloalkanols variable ring sizes are achieved under visible-light irradiation, producing wide range γ,δ-, δ,ε-, even more ketones in good yields, with hydrogen gas as sole byproduct. The produced versatile building blocks, which can be easily converted to other valuable molecules.

Язык: 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, Год журнала: 2023, Номер 500, С. 215522 - 215522

Опубликована: Ноя. 9, 2023

Язык: Английский

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