Visible-Light-Induced Energy-Transfer-Mediated Hydrofunctionalization and Difunctionalization of Unsaturated Compounds via Sigma-Bond Homolysis of Energy-Transfer Acceptors

ACS Catalysis, Год журнала: 2025, Номер 15(3), С. 1854 - 1941

Опубликована: Янв. 17, 2025

Over the past decade, visible-light-mediated energy-transfer (EnT) catalysis, particularly triplet–triplet (TTEnT) has emerged as a mild and environmentally friendly approach for diverse organic synthetic transformations. In contrast to photoredox which typically requires sacrificial electron donors or acceptors complete catalytic cycle, EnT photocatalysis generally proceeds with high atom economy while minimizing generation of wasteful byproducts. Furthermore, successful catalysis is contingent upon precise control redox potentials both photocatalysts substrates, strategies are primarily influenced by triplet energy compatibility between these entities. Considering growing importance photocatalysis, well hydrofunctionalization difunctionalization reactions in synthesis, this review systematically summarizes significant advancements EnT-enabled unsaturated compounds via sigma-bond homolysis over decade. Special emphasis placed on elucidating substrate scopes mechanistic scenarios. Additionally, discusses versatile applications methodologies addresses current challenges opportunities within evolving research field. This structured into six main categories based different types sigma-bonds undergoing homolysis. These include transformations mediated 1) N–O bond oxime esters other N,O-radical precursors; 2) N–S N-sulfonyl imines N,S-radical 3) chalcogen–chalcogen disulfides oxy/thio/selenosulfonates; 4) C–S tri/difluoromethylated sulfinates, acetylenic triflones, arylsulfonium salts; 5) C–X (X = halogen) halides; 6) acceptors. Through providing theoretical backgrounds along comprehensive overview currently employed acceptors, photosensitizers, contemporary EnT-induced compounds, aims serve an invaluable resource future innovations rapidly

Язык: Английский

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Photoredox-Catalyzed Alkene Acylesterification with Acyloxime Esters via C–C and Tertiary C–O Bond Formation

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Янв. 7, 2025

We describe an efficient acyl esterification method for alkenes utilizing acyloxime esters as bifunctional reagents featuring radical acylation and congested C–O bond formation. This approach is characterized by mild photoredox conditions, high step atom economy, a broad substrate scope, excellent regioselectivity. A variety of valuable α-acyl hindered alcohol esters, including those obtained via gram-scale synthesis late-stage functionalization pharmaceutical molecules, were presented, demonstrating its synthetic potential practicability.

Язык: Английский

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Recent Advances in Catalytic Nitrogen–Nitrogen Bond Formation Reactions

ACS Catalysis, Год журнала: 2024, Номер 14(8), С. 5735 - 5778

Опубликована: Апрель 1, 2024

The lack of effective strategies for direct construction nitrogen–nitrogen bonds has hampered developments in the synthesis and application molecules containing hydrazine or azo motifs. Attracted by their properties both material science medicinal chemistry, more attention been drawn to this area, resulting fast growth design azaheterocycles substituted hydrazines. This review focuses on efficient catalytic approaches toward formation N–N N═N through different strategies, including oxidative dehydrogenation, nitrene-transfer reaction, reductive coupling, some other recently developed methods.

Язык: Английский

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Visible-Light-Induced Siloxycarbene Addition to N═N of Azodicarboxylates: Synthesis of Acyl Hydrazides from Acylsilanes

Organic Letters, Год журнала: 2024, Номер 26(10), С. 2039 - 2044

Опубликована: Март 4, 2024

We report the synthesis of acyl hydrazides from acylsilanes in presence visible light without aid additives or transition metals. Acylsilanes underwent [1,2]-Brook rearrangement to generate nucleophilic siloxycarbenes which on further addition N═N azodicarboxylates produced hydrazides. Control experiments indicate that reaction proceeds through singlet carbene intermediate. Transformation hydrazide functionality other functional groups was demonstrated, including drug candidate Moclobemide.

Язык: Английский

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Recent Advances in Strategies for Halide Atom Transfer (XAT) and Their Applications

Chinese Journal of Organic Chemistry, Год журнала: 2024, Номер 44(6), С. 1733 - 1733

Опубликована: Янв. 1, 2024

Язык: Английский

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Photocatalytic selective 1,4-oxyimination/diamination across C=C and N=N bonds to access structurally diverse N-N-N triazane derivatives

Green Synthesis and Catalysis, Год журнала: 2024, Номер unknown

Опубликована: Авг. 1, 2024

A highly selective and atom-economical multi-component remote difunctionalization strategy has been successfully developed. This utilizes precise control over the radical properties of bifunctional precursors electronic traits olefins diazenes to achieve effective radical-mediated 1,4-oxyimination/diamination across C=C N=N bonds. By capitalizing on compatibility reactivity tuning, this approach enables synthesis complex triazine compounds with an N-N-N framework, providing a versatile tool for constructing diverse molecular structures. metal-free method is atom-efficient adaptable various substrates, demonstrating remarkable tolerance broad range functional groups.

Язык: Английский

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Efficient and regioselective C=S bond difunctionalization through a three-component radical relay strategy

Chinese Chemical Letters, Год журнала: 2024, Номер unknown, С. 110424 - 110424

Опубликована: Сен. 1, 2024

Язык: Английский

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MeOH-Triggered Halogen-Atom Transfer of Unactivated Alkyl Bromides Enabling the Photoredox Giese Addition

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 18, 2025

Herein, a nickel-catalyzed, photoredox Giese addition reaction with readily accessible alkyl bromides, driven by available feedstock MeOH as the halogen-atom transfer (XAT) reagent, was successfully achieved under mild conditions. The versatility of this protocol demonstrated through range structurally varied bromides and Giese-type acceptors moderate to good yields. Mechanistic investigation highlights that formation radicals XAT tentatively prompted •CH2OH, which derived from sequential photo-oxidation/1,2-hydrogen-atom MeOH.

Язык: Английский

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Development of N-centered radical scavengers that enables photoredox-catalyzed transition-metal-free radical amination of alkyl pinacol boronates

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Апрель 4, 2025

In recent years, amination of alkylboronates through ionic copper catalysis or boron-ate complex 1,2-metalation has been well established, but complementary radical processes remain less studied before. Herein, based on rational design, we develop several imine-type N-centered scavengers and apply them to the alkylboronates. The reaction proceeds under mild photoredox-catalyzed transition-metal-free conditions features excellent functional group tolerance. It also enables preparation a range medicinally valuable amine derivatives from natural products. Further application this reagent in C-H amination, deoxygenative decarboxylative three component trifluoromethylative/sulfonylative aminations are realized. mechanistic studies DFT calculations conducted provide detailed evidence for mechanism.

Язык: Английский

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Photocatalytic Ring-Closing Metathesis/Amination of 1,6-Enynes and 1,7-Enynes: Synthesis of α,β-Unsaturated γ-Lactams and Quinolin-2-ones

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Май 20, 2025

A photocatalyzed ring-closing metathesis/amination of 1,6-enynes and 1,7-enynes using alkyl oxime esters as both an alkene deconstruction auxiliary amination source is present for the synthesis α,β-unsaturated γ-lactams quinolin-2-ones. Preliminary mechanistic studies suggest that intramolecular 1,5-hydrogen atom transfer key to generation unstabilized radicals, which subsequently promote homolytic Cα-Cβ cleavage under driving force formation more stable captodative radicals.

Язык: Английский

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