Light-induced ligand-to-metal charge transfer of Fe(III)-OR species in organic synthesis

Organic & Biomolecular Chemistry, Год журнала: 2024, Номер 22(30), С. 6034 - 6044

Опубликована: Янв. 1, 2024

This review highlights studies on ligand-to-metal charge transfer of Fe( iii )-OR species in organic transformations.

Язык: Английский

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Unified Photocatalytic Strategy for the Cross-Coupling of Alcohols with Aryl Halides Enabled by Synergistic Nickel and Iron LMCT Catalysis

ACS Catalysis, Год журнала: 2024, Номер 14(17), С. 12757 - 12768

Опубликована: Авг. 9, 2024

The use of alcohol feedstock as a coupling partner in cross-coupling reactions offers an extraordinary potential for the efficient synthesis Csp3-rich complex molecular scaffolds. This prominent strategy relies on generation alkoxy radicals, which can react via various radical pathways to give carbon-centered radicals that be engaged C–C bond formation reactions. However, involving catalytic directly from native alcohols are highly challenging and scope existing methods remains particularly limited. Moreover, unified incorporate broad range with aryl halides is currently unavailable. Herein, we report general photocatalytic platform combines nickel iron ligand-to-metal charge transfer (LMCT) catalysis selective deconstructive Csp3–Csp3 cleavage arylation unactivated alcohols. protocol leverages ability photoinduced LMCT generate diversely substituted alcohols, enabling implementation bond-forming manifolds. These include dehydroxymethylative aliphatic remote cyclic yield alkyl ketones, methylation using tertiary methyl source. methodology practical engaging large variety commercially available under mild conditions, abundant catalysts. Mechanistic studies, including stoichiometric organometallic chemistry voltammetry, provide insights into crucial role ancillary ligand surrounding catalyst stabilizing both low- high-valent intermediates.

Язык: Английский

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Photoinduced C(sp³)–H Chalcogenation of Amide Derivatives and Ethers via Ligand-to-Metal Charge-Transfer

Organic Letters, Год журнала: 2022, Номер 24(25), С. 4524 - 4529

Опубликована: Июнь 21, 2022

A photoinduced, iron(III) chloride-catalyzed C-H activation of

Язык: Английский

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

Synthesis, Год журнала: 2023, Номер 56(13), С. 1967 - 1978

Опубликована: Ноя. 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

Язык: Английский

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The Merger of Halogen Atom Transfer (XAT) and Energy Transfer Catalysis (EnT) for the Modular 1,2-Iminylalkylation of Diazenes

Organic Letters, Год журнала: 2023, Номер 25(38), С. 7009 - 7013

Опубликована: Сен. 14, 2023

The 1,2-iminylalkylation of diazenes using alkyl iodides in combination with an O-benzoyl oxime is reported. In this transformation, acted as a radical precursor and XAT mediator. addition to common iodides, other such iodomethane, iodomethane-d3, trifluoroiodomethane, ethyl difluoroiodoacetate, iodoalkanes containing unprotected hydroxyl amide groups can also serve C-radical precursors the electrophilic acceptors.

Язык: Английский

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