Visible Light Induced Photocatalyst‐Free C−X (X=B, C, O, P,S, Se) Bond Formation of Aryl Halides

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(8), P. 1719 - 1737

Published: Feb. 29, 2024

Abstract Aryl halides are one of the most important chemical feedstocks in pharmaceuticals due to its easy accessibility, inexpensiveness, and widely utilized as aryl radical precursors organic synthetic chemistry. Conventionally, stoichiometric reagents such AIBN/n‐Bu 3 SnH were used for generation from halides, suffered requirement toxic initiators, high temperature thus, development simple, mild strategies highly desirable. Recently, visible light mediated received considerable attention, allowing under reaction conditions. The present review described recent breakthroughs advancements photocatalyst‐free C−B/C/O/P/Se/S bond formation halides.

Language: Английский

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Neutral Chalcogen Bonding Enabled Photoinduced Cross‐Electrophile C—S/Se Coupling of Aryl Iodides via S_RN1 Process

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 7, 2025

Comprehensive Summary Cross‐coupling reactions between aryl halides and thiolates or selenolates typically require transition metals, photocatalysts, strong bases, or/and malodorous thiols/selenols, with various mechanisms proposed. This study aims to leverage a new application of neutral ChB address these challenges enable very simple photoinduced cross‐electrophile C—S/Se coupling using readily available chalcogen electrophiles. Mechanistic investigations have revealed the important role in facilitating single electron transfer processes, thereby enabling generation thiolates/selenolates from stable electrophiles α ‐aminoalkyl radicals, which possess capability abstract halogen atoms iodides. Moreover, provided support for radical nucleophilic substitution mechanism.

Language: Английский

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Sustainable Synthesis through Catalyst‐Free Photoinduced Cascaded Bond Formation

Chemistry - An Asian Journal, Journal Year: 2024, Volume and Issue: 19(14)

Published: May 8, 2024

The beginning of photochemical reactions revolutionized synthetic chemistry through sustainable practices. This review explores cutting-edge developments in leveraging light-induced processes for generating cascaded C-C and C-hetero bonds without catalysts. Significantly, catalyst-free photoinduced methodologies have garnered considerable attention, especially the creation varied heterocyclic frameworks drug design synthesis natural products. article delves into underlying mechanisms, addresses limitations, evaluates various methodologies, emphasizing potential photocatalyst transition metal-free to enhance sustainability. Divided two sections, it covers recent strides C-heteroatom multiple bond formation reactions.

Language: Английский

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Visible Light-Induced Radical Cascade Functionalization of Quinoxalin-2(1H)-ones: Three-Component 1,2-Di(hetero)arylation Approach with Styrenes and Thianthrenium Salts

Organic Letters, Journal Year: 2024, Volume and Issue: 26(41), P. 8821 - 8826

Published: Oct. 9, 2024

The additive-free visible light-induced three-component 1,2-di(hetero)arylation of styrenes was developed using quinoxalin-2(1

Language: Английский

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Recent Progress in C–S Bond Formation via Electron Donor-Acceptor Photoactivation

Organic & Biomolecular Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This review summarizes recent progress in EDA complex-promoted C–S bond formation using various sulfur-containing substrates under mild conditions via visible light irradiation.

Language: Английский

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Access to β‐Lactam Sulfonamides from Sulfamoyl Chlorides via Photoredox Catalyzed C−S Bond Formation

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(15), P. 3310 - 3315

Published: June 13, 2024

Abstract Sulfonyl chlorides are a synthetically attractive source of sulfonyl radicals in photoredox catalysis and useful precursors the synthesis sulfones. Sulfamoyl chlorides, on other hand, remain poorly represented despite their similar potential. In this study, N ‐chlorosulfonylated β‐lactams were prepared from readily available utilized an atom transfer radical addition (ATRA) reaction with variety olefins, producing β‐lactam sulfonamides 49–95% yields. β‐Lactams fused to dihydro‐1,2‐thiazine ring which closely resemble carbacephems, widely used class antibiotics, also synthesized by intra‐molecular ATRA reaction. This methodology enables preparation sulfonamides, compounds that great interest pharmacology.

Language: Английский

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Visible-light-induced aerobic C-3 thiocyanation of indoles using porphyrin as photoredox catalyst

Synthetic Communications, Journal Year: 2025, Volume and Issue: unknown, P. 1 - 12

Published: March 19, 2025

In this work, we report a metal-free and environmentally friendly approach for the electrophilic C–H thiocyanation of indoles under visible light irradiation. Using porphyrin as photocatalyst atmospheric air an oxidant, developed mild efficient route to synthesize series thiocyanate products with both electron-rich electron-deficient systems in moderate good yields. The use radical scavenger like TEMPO helped establish photoredox mechanism. This method offers sustainable promising synthesizing heterocyclic substrates, aromatics, bioactive molecules through catalysis.

Language: Английский

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Visible-Light-Promoted C3-Sulfenylindoles with Arylsulfonyl Chlorides via Electron Donor–Acceptor Complex

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(11), P. 7591 - 7597

Published: May 9, 2024

In this study, we present an efficient approach for the synthesis of 3-sulfenyl indoles through electron donor–acceptor (EDA) complex-promoted photoreaction. This sulfenylation reaction leverages sulfonyl chlorides as sulfur source and employs PPh3 reductant without need any transition-metal catalyst or photocatalyst. At same time, relaxation process excited EDA complex was theoretically investigated at method multiconfiguration second-order perturbation//complete active space self-consistent field/PCM level theory, which involves π bond injecting to antibonding orbital S–Cl in arylsulfonyl chlorides.

Language: Английский

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Exogenous Photocatalyst-Free Aryl Radical Generation from Diaryliodonium Salts and use in Metal-Catalyzed C–H Arylation

Published: March 20, 2024

Herein, we demonstrate 1) that Lewis base heteroatom coordination to diaryliodonium salts is not required for light-driven radical generation and 2) radicals generated by this route can be captured transition-metals coupling reactions. These results are the first step toward developing new aryl reactions without exogenous photocatalysts.

Language: Английский

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Transition-Metal- and Photocatalyst-Free Photoinduced Formation of Carbon–Pnictogen (–N, –P) Bonds

Synthesis, Journal Year: 2024, Volume and Issue: 56(17), P. 2627 - 2637

Published: April 2, 2024

Abstract Pnictogens, classified within group 15 elements, play a pivotal role in the constitution of diverse array drug molecules, natural products, and functional materials. Recent research has increasingly prioritized exploration mild conditions for synthesizing C–Pnictogen (C–N C–P) bonds, highlighting growing emphasis on efficient sustainable synthetic methodologies. This Short Review explores fundamental mechanisms, addresses constraints, assesses methodologies, underscoring potential photocatalyst- transition-metal-free photochemical reactions advancing sustainability. Divided into two segments, it encompasses recent advancements facilitating C–N C–P bond formation. 1 Introduction 2 Carbon–Nitrogen (C–N) Bond Formation 3 Carbon–Phosphorus (C–P) 4 Summary Outlook

Language: Английский

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