Photoredox catalysis using methoxyarenes: mechanistic studies and synthetic applications DOI
Masanori Tayu, Kakeru Matsukuma,

Tomohisa Yamaguchi

и другие.

Bulletin of the Chemical Society of Japan, Год журнала: 2024, Номер 97(12)

Опубликована: Ноя. 28, 2024

Abstract Bismethoxybinaphthyl was demonstrated to be an effective photoredox catalyst. This study explored the utility of bismethoxybinaphthyl catalysts in various reactions, including trifluoromethylation, C–H imidation, intramolecular lactonization, benzylation, and reductive coupling via 1-electron reduction carbonyl groups. Electrochemical analyses were conducted determine redox potential catalyst, revealing its notably stronger reducing power compared with representative organic catalysts. Furthermore, spectroscopic studies performed elucidate mechanism photoinduced electron transfer. It found that does not form donor–acceptor complex; instead, it facilitates transfer through a locally excited state.

Язык: Английский

Molecular Photoelectrocatalysis for Radical Reactions DOI
Peng Xiong, Hai‐Chao Xu

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Янв. 13, 2025

ConspectusMolecular photoelectrocatalysis, which combines the merits of photocatalysis and organic electrosynthesis, including their green attributes capacity to offer novel reactivity selectivity, represents an emerging field in chemistry that addresses growing demands for environmental sustainability synthetic efficiency. This synergistic approach permits access a wider range redox potentials, facilitates transformations under gentler electrode decreases use external harsh reagents. Despite these potential advantages, this area did not receive significant attention until 2019, when we others reported first examples modern molecular photoelectrocatalysis. These studies showcased immense hybrid strategy, only inherits strengths its parent fields but also unlocks unprecedented enabling challenging mild conditions while minimizing reliance on stoichiometric oxidants or reductants.In Account, present our efforts develop photoelectrocatalytic strategies leverage homogeneous catalysts facilitate diverse radical reactions. By integrating electrocatalysis with key photoinduced processes such as single electron transfer (SET), ligand-to-metal charge (LMCT), hydrogen atom (HAT), have established methods transform substrates organotrifluoroborates, arenes, carboxylic acids, alkanes into reactive intermediates. intermediates subsequently engage heteroarene C-H functionalization Importantly, photoelectrochemical catalysts, generated bulk solution readily participate efficient reactions without undergoing further overoxidation carbocations, common challenge conventional electrochemical systems.By integration photoelectrocatalysis asymmetric catalysis, developed catalysis (PEAC), proves be enantioselective synthesis chiral nitriles. involves two relay catalytic cycles: initial process engenders benzylic radicals from precursors alkyl aryl alkenes, C-radicals are then subjected cyanation subsequent copper-electrocatalytic cycle.Within realm oxidative transformations, anode serves crucial component recycling generating photocatalyst, cathode promotes proton reduction. dual functionality enables via H

Язык: Английский

Процитировано

3
Adoption of Electrochemistry within the Pharmaceutical Industry: Insights from an Industry-Wide Survey DOI
Antonio C. Ferretti, Benjamin Cohen, Lin Deng

и другие.

Organic Process Research & Development, Год журнала: 2025, Номер unknown

Опубликована: Янв. 27, 2025

Язык: Английский

Процитировано

2
Organo-mediator enabled electrochemical transformations DOI
Wei-Mei Zeng, Yanwei Wang,

Chunhui Peng

и другие.

Chemical Society Reviews, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

This review highlights organo-mediators that enable electrochemical reactions via outer-sphere electron transfer (ET), offering advantages such as availability, tunability, and simplified post-processing compared to direct electrolysis.

Язык: Английский

Процитировано

1
Unlocking HFIP for Fluoroalkylation with Molecular Photoelectrocatalysis DOI Open Access
Yueqin Zheng, Yuxing Gao, Peng Xiong

и другие.

Angewandte Chemie International Edition, Год журнала: 2025, Номер unknown

Опубликована: Янв. 23, 2025

Despite the increasing interest in radical-based fluoroalkylation techniques, organofluorine compounds bearing partially fluorinated hexafluoroisopropyl group remain extremely scarce due to lack of appropriate reagents. Herein we report an unprecedented photoelectrocatalytic method for C-H hexafluoroisopropylation indoles and tryptophan peptides, utilizing readily available hexafluoro-2-propanol (HFIP) as reagent. In this process, HFIP is converted into radicals, enabling reactions. This study broadens potential applications molecular photoelectrocatalysis, highlighting its capacity enable transformations that are difficult accomplish through traditional electrochemical or photochemical approaches.

Язык: Английский

Процитировано

0
Overcoming High Reduction Potentials via Consecutive Mechanical-Force-Induced Electron Transfer Strategy DOI Creative Commons
Zhong Lian, Xiaohong Wang, X. He

и другие.

Research Square (Research Square), Год журнала: 2025, Номер unknown

Опубликована: Фев. 5, 2025

Abstract Mechanical-force-induced redox catalysis has recently advanced rapidly, emerging as a green and innovative tool in synthetic chemistry. The foundation of this strategy lies the single electron transfer (SET) from polarized piezoelectric materials to substrates, which is initiated by potential generated through mechanical agitation. magnitude primarily influenced intrinsic properties material. In certain circumstances, however, may be insufficient trigger SET process, akin limitations visible-light excitation photocatalytic reactions. This challenge motivated us explore effective solutions. work, we establish catalytic system that utilizes consecutive mechanical-force-induced (ConMET) strategy. novel employs mechanochemical catalysts, with 9-phenyl-dihydroacridine (D1) serving sacrificial donors, facilitating produce significantly more powerful reductive species during grinding. Our approach effectively promotes reduction aryl iodides, bromides even electron-rich chlorides, possess potentials high − 2.8 V (vs. SCE), leading formation radicals. Ultimately, enables anti-Markovnikov hydroarylation alkenes dehalogenative deuteration aromatic halides (Cl, Br) under mild conditions.

Язык: Английский

Процитировано

0
Photoelectrocatalytic Cl-mediated C(sp3)–H aminomethylation of hydrocarbons by BiVO4 photoanodes DOI Creative Commons

Anzai Shi,

Pengfei Xie, Yanwei Wang

и другие.

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

Опубликована: Март 8, 2025

Interfacial photoelectrochemistry at photoanodes has been extensively researched for solar energy conversion, but its application the production of high-value-added chemical compounds in organic chemistry still presents challenges. Herein, we report photoelectrocatalytic Cl-mediated C(sp3)–H aminomethylation alkanes with self-developed and reusable BiVO4 photoanodes. The swift condensation aniline aldehydes, along decrease electricity input by photogenerated holes photoanodes, work together to prevent excessive oxidation aniline, leading high yields desired product. Mechanistic experiments demonstrate that Cl- ions, as key mediators, could be attracted oxidized form Cl2. This is followed light-promoted homolytic cleavage Cl2, generating Cl radicals efficiently abstract hydrogen atoms from hydrocarbons. opens an avenue interfacial photoelectrochemical synthesis demonstrates a potential method optimizing conversion into fuels. A stable recyclable photoelectrode material was developed efficient hydrocarbons cell, which provides promising fuel conversion.

Язык: Английский

Процитировано

0
Photoelectrochemistry-Promoted Ni-Catalyzed C–O Cross-Couplings DOI Creative Commons

Zhao‐Ran Liu,

Ye Wang, Cong Ma

и другие.

Precision Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Апрель 10, 2025

Язык: Английский

Процитировано

0
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

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Апрель 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.

Язык: Английский

Процитировано

0
Interplay Between Molecular Electrochemistry and Light in Mechanistic Investigations DOI
Éric Labbé, Olivier Buriez

Current Opinion in Electrochemistry, Год журнала: 2024, Номер 49, С. 101613 - 101613

Опубликована: Ноя. 22, 2024

Язык: Английский

Процитировано

0
Photoredox catalysis using methoxyarenes: mechanistic studies and synthetic applications DOI
Masanori Tayu, Kakeru Matsukuma,

Tomohisa Yamaguchi

и другие.

Bulletin of the Chemical Society of Japan, Год журнала: 2024, Номер 97(12)

Опубликована: Ноя. 28, 2024

Abstract Bismethoxybinaphthyl was demonstrated to be an effective photoredox catalyst. This study explored the utility of bismethoxybinaphthyl catalysts in various reactions, including trifluoromethylation, C–H imidation, intramolecular lactonization, benzylation, and reductive coupling via 1-electron reduction carbonyl groups. Electrochemical analyses were conducted determine redox potential catalyst, revealing its notably stronger reducing power compared with representative organic catalysts. Furthermore, spectroscopic studies performed elucidate mechanism photoinduced electron transfer. It found that does not form donor–acceptor complex; instead, it facilitates transfer through a locally excited state.

Язык: Английский

Процитировано

0