Alkyl radicals from diacyl peroxides: metal-/base-/additive-free photocatalytic alkylation of N-heteroaromatics

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(20), P. 7971 - 7977

Published: Jan. 1, 2023

Alkyl diacyl peroxides were demonstrated to be efficient alkylating reagents for the visible-light-induced 4CzIPN-catalyzed direct C–H alkylation of N -heteroaromatics.

Language: Английский

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Photocatalytic C(sp²)–H sulfamoylation of enamides: regio- and stereoselective construction of (E)-β-sulfamoyl enamides

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(21), P. 5470 - 5477

Published: Jan. 1, 2023

A photocatalytic, regio- and stereoselective olefinic β-C–H sulfamoylation of enamides with commercially available sulfamoyl chlorides was developed.

Language: Английский

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Pd-Catalyzed C–O Bond Formation: Coupling of Aryl Boronic Acids with O-Electrophiles

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 3636 - 3646

Published: Feb. 14, 2025

Language: Английский

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Phenothiazine Sulfoxides as Active Photocatalysts for the Synthesis of γ-Lactones

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 2, 2025

N-substituted phenothiazines are prominent and highly effective organic photoredox catalysts, particularly known for their strong reducing capabilities. Despite wide utility, the closely related phenothiazine sulfoxides, which easily form upon oxidation, have been largely overlooked not explored in context of photocatalysis. Herein, we describe discovery application N-phenylphenothiazine sulfoxide as a photocatalyst reductive activation cyclic malonyl peroxides, giving access to complex γ-lactones starting from simple olefins. Detailed mechanistic studies were carried out better understand situ formation active catalyst species commercial precursor, well interconversion photocatalytic mechanism γ-lactone products. Specifically, employed broad range tools, including time-resolved spectroscopy, spectroelectrochemistry, transient UV-vis absorption voltammetry, isotopic labeling, radical trapping experiments, NMR density functional theory (DFT) calculations. The synthetic utility this protocol is demonstrated substrate scope study, highlighting facile spirocyclic γ-lactones, widely recognized biological importance.

Language: Английский

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Photo‐Induced C−H Methylation Reactions

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(72)

Published: Oct. 6, 2023

Direct C-H methylation is a highly valuable approach for introducing methyl groups into organic molecules, particularly in pharmaceutical chemistry. Among the various methodologies available, photo-induced stands out as an exceptional choice due to its mild reaction conditions, energy efficiency, and compatibility with functional groups. This article offers comprehensive review of photochemical strategies employed direct selective C(sp3 )-H, C(sp2 C(sp)-H bonds molecules. The discussed encompass transition-metal-based photocatalysis, organophotocatalysis, well other metal-free approaches, including electron donor-acceptor (EDA)-enabled transformations. Importantly, wide range easily accessible agents such tert-butyl peroxide, methanol, DMSO, ether, TsOMe, N-(acetoxy)phthalimide, acetic acid, halides, even methane can serve effective methylating reagents modifying diverse targets. These advancements are anticipated drive further progress fields synthesis, development, opening up exciting avenues creating novel molecules discovering new drug compounds.

Language: Английский

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Cyclic Sulfoximines as Methyl and Perdeuteromethyl Transfer Agents and Their Applications in Photoredox Catalysis

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(51)

Published: Sept. 5, 2024

Benzo[1,3,2]dithiazole-1,1,3-trioxides are bench-stable and easy-to-use reagents. In photoredox catalysis, they generate methyl perdeuteromethyl radicals which can add to a variety of radical acceptors, including olefins, acrylamides, quinoxalinones, isocyanides, enol silanes, N-Ts acrylamide. As byproduct, salt is formed be regenerated the original methylating agent. Flow chemistry provides an option for reaction scale-up further underscoring synthetic usefulness these methylation Mechanistic investigations suggest single-electron transfer (SET) pathway induced by catalysis.

Language: Английский

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Copper- or iron-catalyzed stereoselective methylation of enamides using dicumyl peroxide as the methyl source

New Journal of Chemistry, Journal Year: 2023, Volume and Issue: 47(36), P. 17060 - 17065

Published: Jan. 1, 2023

An efficient and versatile copper- or iron-catalyzed direct stereoselective β-C(sp 2 )–H methylation of enamides by using dicumyl peroxide (DCP) as the methylating reagent has been developed.

Language: Английский

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Coordinating activation strategy enables 1,2-alkylamidation of alkynes

Chemical Science, Journal Year: 2023, Volume and Issue: 14(41), P. 11466 - 11473

Published: Jan. 1, 2023

The radical 1,2-difunctionalization reaction of alkynes has been evolved into a versatile approach for expeditiously increasing the complexity common feedstock alkyne. However, intermolecular 1,2-carboamidation with general alkyl groups is an unsolved problem. Herein, we show that coordinating activation strategy could act as efficient tool enabling 1,2-alkylamidation alkynes. With employment diacyl peroxides both alkylating reagents and internal oxidants, large library β-alkylated enamides constructed in three-component manner from readily accessible amides This protocol exhibits broad substrate scope good functional group compatibility amenable late-stage functionalization natural molecules biologically compounds.

Language: Английский

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Photoredox-Catalyzed C–H Methylation of N-Heteroarenes Enabled by N,N-Dimethylethanolamine

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 21, 2024

A visible-light-driven radical C-H methylation of

Language: Английский

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