Visible-Light Induced and Iron Peroxo-Promoted Radical Difunctionalization of Alkene for the Synthesis of β-Ketosulfone and α-Chloroketone DOI
Xinyu Zhu, Chen Bao, Xingxian Zhang

et al.

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

Published: Dec. 26, 2024

In this work, a switchable synthesis of β-ketosulfone and α-chloroketone through radical difunctionalization alkenes is reported. The transformation works well under iron peroxo species/photoredox dual catalysis an open-flask atmosphere, the reaction highlighted with good yields broad scope. Mechanism studies show that initiated by formal [4 + 2] cyclization sulfonyl in regioselective manner.

Language: Английский

Iron-Catalyzed Aerobic Carbonylation of Methane via Ligand-to-Metal Charge Transfer Excitation DOI Creative Commons
Hui Pan, Qing An, Binh Khanh

et al.

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

Published: Jan. 6, 2025

The integration of ligand-to-metal charge transfer (LMCT) catalytic paradigms with radical intermediates has transformed the selective functionalization inert C-H bonds, facilitating use nonprecious metal catalysts in demanding transformations. Notably, aerobic carbonylation methane to acetic acid remains formidable due rapid oxidation methyl radicals, producing undesired C1 oxygenates. We present an iron terpyridine catalyst utilizing LMCT achieve exceptional C2/C1 selectivity through synergistic photoexcitation, generation, and carbonylation. Mechanistic studies highlight critical roles Fe(II) Fe-carbonyl complexes bypassing via a rebound-like pathway, unlocking unprecedented efficiency

Language: Английский

Citations

2
Decarboxylative Cross-Coupling Enabled by Fe and Ni Metallaphotoredox Catalysis DOI Creative Commons
Reem Nsouli, Sneha Nayak, Venkadesh Balakrishnan

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(43), P. 29551 - 29559

Published: Oct. 18, 2024

Decarboxylative cross-coupling of carboxylic acids and aryl halides has become a key transformation in organic synthesis to form C(sp

Language: Английский

Citations

4
Synergistic LMCT and Ni Catalysis for Methylative Cross-Coupling Using tert-Butanol: Modulating Radical Pathways via Selective Bond Homolysis DOI
Lingfei Duan, Yunzhi Lin, Qing An

et al.

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

Published: April 18, 2025

Ligand-to-metal charge transfer (LMCT) excitation has emerged as a potent strategy for the selective generation of heteroatom-centered radicals, yet its full potential in modulating open-shell radical pathways remains underexplored. Here, we present photocatalytic methylative cross-coupling reaction that capitalizes on synergistic interplay between LMCT and Ni catalysis, enabling use tert-butanol an efficient benign methylating reagent. The electron-deficient ligand 2,6-ditrifluoromethyl benzoate facilitates Ce(IV)-mediated bond scission tert-butanol, generating methyl is subsequently captured by catalytic cycle to form C-CH3 bonds. Under mild conditions, this affords methylation sp3 carbons adjacent carbonyls sp2 centers, demonstrating broad functional group tolerance applicability late-stage functionalization bioactive molecules. Additionally, trideuteromethylative coupling can be facilely achieved using commercial tert-butanol-d10. This approach circumvents need traditional tert-butoxy precursors, such peroxides, while strategically pathway favor β-scission suppress unwanted formation solution. Mechanistic studies reveal plays crucial role facilitating generation, supporting concerted Ce-OR β-C-C homolysis mechanism, further evidenced modulation regioselectivity alkoxy radical-mediated β-scission.

Language: Английский

Citations

0
Photoinduced Ligand-to-Metal Charge Transfer (LMCT) in Organic Synthesis: Reaction Modes and Research Advances DOI
Yingying Yang, Xinxiang Huang, Yi Jin

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 20, 2024

In recent years, visible light-induced ligand-to-metal charge transfer (LMCT) has emerged as an attractive approach for synthesizing a range of functionalized molecules. Compared to conventional photoredox reactions, photoinduced LMCT activation does not depend on redox potential and offers diverse reaction pathways, making it particularly suitable the inert bonds functional modification complex organic This review highlights indispensable role in synthetic chemistry, with focus advancements LMCT-mediated hydrogen atom (HAT), C-C bond cleavage, decarboxylative transformations, radical ligand (RLT) reactions.

Language: Английский

Citations

1
Visible-Light Induced and Iron Peroxo-Promoted Radical Difunctionalization of Alkene for the Synthesis of β-Ketosulfone and α-Chloroketone DOI
Xinyu Zhu, Chen Bao, Xingxian Zhang

et al.

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

Published: Dec. 26, 2024

In this work, a switchable synthesis of β-ketosulfone and α-chloroketone through radical difunctionalization alkenes is reported. The transformation works well under iron peroxo species/photoredox dual catalysis an open-flask atmosphere, the reaction highlighted with good yields broad scope. Mechanism studies show that initiated by formal [4 + 2] cyclization sulfonyl in regioselective manner.

Language: Английский

Citations

0