Visible-Light-Mediated Vicinal Dihalogenation of Unsaturated C–C Bonds Using Dual-Functional Group Transfer Reagents DOI Creative Commons
Rahul Giri, Egor S. Zhilin,

Mathias Kissling

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(46), P. 31547 - 31559

Published: Nov. 5, 2024

The growing demand for chemical production continues to drive the development of sustainable and efficient methods introducing molecular complexity. In this context, exploration unconventional functional group transfer reagents (FGTRs) has led significant advancements in practical atom-efficient synthetic protocols. Aiming advance field valuable organic synthesis, herein we report successful carbon-based, bench-stable, modular, inexpensive implemented dual halogen unsaturated hydrocarbons via photocatalytic activation based on a radical-polar crossover mechanism. This method beneficially enables vicinal dichlorination, dibromination, bromo-chlorination reactions olefins, offering alternatives use toxic binary halogens. Detailed mechanistic studies, combining experimental, spectroscopic, theoretical investigations, revealed distinctive single-electron reduction FGTR. process triggers mesolytic carbon–halogen bond cleavage, followed by radical 1,2-halide rearrangement, leading continuous generation dihalogen species reaction medium. wide applicability developed protocol is demonstrated through an extensive scope molecules, including additional operations strain-release dihalogenation.

Language: Английский

Recent Progress in Visible Light‐Mediated Synthesis of γ‐lactams DOI Open Access
Suman Pradhan, Shoubhik Das

Helvetica Chimica Acta, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 30, 2025

Abstract The integration of sustainable practices, such as employing renewable light sources for synthesizing valuable synthetic scaffolds, has been progressing over the past few decades. Among these noteworthy organic frameworks, lactams, particularly γ‐lactams, have established their prominence due to extensive applications in pharmaceutical, agricultural, and medicinal domains. This growing significance γ‐lactams spurred considerable interest synthesis, especially via milder, more sustainable, environmentally friendly methods. In recent years, numerous innovative reaction mechanisms explored, highlighting how photocatalysis can enable formation from readily accessible precursors through C−N bond cyclization processes. review emphasizes potential photocatalytic strategies not only enhance current methods but also foster development greener chemical processes future.

Language: Английский

Citations

0
Photochemical Dual Radical Coupling of Carboxylates with Alkenes/Heteroarenes via Diradical Equivalents DOI
Guanjie Wang,

Jingxin Ding,

J. Wu

et al.

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

Published: March 24, 2025

Carboxylate diradical intermediates, with α-carbon and carboxylic oxygen acting as reactive radical centers, represent a highly attractive long-sought species in reaction design synthesis. However, capturing these intermediates for coupling reactions poses formidable challenge due to their inherent instability spontaneous decarboxylation. Here, we addressed this by temporarily masking the carboxylate reactivity via photocleavable dynamic oxygen–iodine bond. This approach effectively prevents unwanted decarboxylation enables controlled utilization of forming new bonds. Carboxylates alkenes/heteroarenes, among most readily available raw materials, can now seamlessly couple pathways form γ-butyrolactones, which are common motifs found numerous natural products bioactive molecules. Ionic traditional carboxylates ruled out based on experimental studies density functional theory (DFT) calculations. strategy overcomes substrate limitations methods, significantly expanding range applicable alkenes/heteroarenes. Our method allows transforming alkenes modes diverse offers insights into developing di- multiradical equivalents unprecedented synthetic designs.

Language: Английский

Citations

0
Phenothiazine Sulfoxides as Active Photocatalysts for the Synthesis of γ-Lactones DOI Creative Commons
Niklas Hölter,

Nils Rendel,

Leander Spierling

et al.

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

Citations

0
Synthesis of trans‐2‐(Disubstituted‐amino)alkenyl Polyoxyperfluoroalkyl Ketones from Tertiary Amines and Perfluoroalkyl Ether Carboxylates Featuring “–CF2O–” Units† DOI
Qijian Ni, Shiyu Zhao, Cheng‐Ying Wu

et al.

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

Published: April 25, 2025

Comprehensive Summary A one‐pot transformation of aliphatic and aromatic tertiary amines to novel fluorinated enaminones has been developed, utilizing perfluoroalkyl ether carboxylates (PFECA salts) featuring “–CF 2 O–” units as the fluorine‐containing reagents. Carbonyl fluoride, acyl fluorides anhydrides by thermal decomposition these PFECA salts were proposed act key active species that trigger tandem oxidation–acylation process amines, through enamine intermediates.

Language: Английский

Citations

0
Visible-Light-Mediated Vicinal Dihalogenation of Unsaturated C–C Bonds Using Dual-Functional Group Transfer Reagents DOI Creative Commons
Rahul Giri, Egor S. Zhilin,

Mathias Kissling

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(46), P. 31547 - 31559

Published: Nov. 5, 2024

The growing demand for chemical production continues to drive the development of sustainable and efficient methods introducing molecular complexity. In this context, exploration unconventional functional group transfer reagents (FGTRs) has led significant advancements in practical atom-efficient synthetic protocols. Aiming advance field valuable organic synthesis, herein we report successful carbon-based, bench-stable, modular, inexpensive implemented dual halogen unsaturated hydrocarbons via photocatalytic activation based on a radical-polar crossover mechanism. This method beneficially enables vicinal dichlorination, dibromination, bromo-chlorination reactions olefins, offering alternatives use toxic binary halogens. Detailed mechanistic studies, combining experimental, spectroscopic, theoretical investigations, revealed distinctive single-electron reduction FGTR. process triggers mesolytic carbon–halogen bond cleavage, followed by radical 1,2-halide rearrangement, leading continuous generation dihalogen species reaction medium. wide applicability developed protocol is demonstrated through an extensive scope molecules, including additional operations strain-release dihalogenation.

Language: Английский

Citations

2