Reassessing the Photochemical Upcycling of Polystyrene Using Acridinium Salts DOI Creative Commons
Ana S. Abreu, Daniel Taton, Dario M. Bassani

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 13, 2024

Abstract Polystyrene ( PS ) is a commodity plastic recalcitrant to chemical recycling or upcycling processes. Approaches aimed at deconstructing by photocatalytic means struggle generate high‐energy species capable of cleaving the robust C−H and C−C bonds . We show that 9‐mesityl‐10‐methylacridinium perchlorate MA various grades substrates into up 40 % benzoic acid BAc ), formic FA small proportions acetophenone ACP under visible light (456 nm) through solar radiation. Time‐resolved emission absorption spectroscopy evidence reaction with oxygen primary photochemical step in oxygen‐saturated solutions, accounting for 77 photons absorbed vs. 1 direct (0.303 M repeating units). These results are agreement mechanism which ‐mediated photo occurs abstraction benzylic H atoms reactive generated energy electron transfer from excited state Addition triplet O 2 these radicals, followed intra‐ inter‐molecular hydrogen atom (HAT) generates C‐ O‐centered radicals then undergoing β‐scission hydroperoxide fragmentation. The formation intermediate oligomers functionalized terminal carbonyl groups demonstrated both infrared analysis MALDI TOF mass spectrometry. undergo further photoinduced conversion even absence , as evidenced size exclusion chromatography irradiated samples.

Language: Английский

Redox Reactions of Organic Molecules Using Rotating Magnetic Field and Metal Rods DOI
Haodong Liu,

Xuliang Han,

Xiaomei Feng

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(26), P. 18143 - 18150

Published: June 25, 2024

In recent years, redox reactions have harnessed light or mechanical energy to enable the formation of chemical bonds. We postulated a complementary approach that electromagnetic induction could promote reaction organic molecules using rotating magnetic field and metal rods. Here, we report electromotive force activates redox-active trifluoromethylating reagents. This magnetoredox system can be applied trifluoromethylation heteroarenes with high regioselectivity hydrotrifluoromethylation alkenes without need for catalysts additives.

Language: Английский

Citations

4
Photo-driven Aerobic C(sp3)-H Oxidation by Organic Photocatalysts: A Recent Review DOI
Mianran Chao, Qin Zhang, Jin Ge

et al.

Tetrahedron, Journal Year: 2025, Volume and Issue: unknown, P. 134496 - 134496

Published: Jan. 1, 2025

Language: Английский

Citations

0
Photoredox catalysis of acridinium and quinolinium ion derivatives DOI
Shunichi Fukuzumi, Yong‐Min Lee, Wonwoo Nam

et al.

Bulletin of the Korean Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 9, 2024

Abstract Photoredox catalysis has attracted increasing attention because of wide range synthetic transformations and solar energy conversion applications. Reviews on photoredox have so far focused predominantly the This review highlights how organic catalysts were developed they function as efficient photocatalysts in mechanistic point views. In particular, 9‐mesityl‐10‐methylactidinium (Acr + –Mes) been highlighted one best catalysts. Acr –Mes was originally a model compound photosynthetic reaction center to mimic long lifetime charge‐separated state which is converted chemical photosynthesis. The reason why acts most catalyst clarified terms one‐electron redox potentials lifetimes electron‐transfer • •+ ) produced upon photoexcitation different solvents. mesityl substituent at 9‐position moiety essential for discussed comparison with acridinium ions substituents R –R) including 10‐methylacridinium ion no (AcrH ). mechanisms are various reactions mimicking quinolinium its derivatives also that –Mes. Finally, immobilization form composite improve catalytic activity stability.

Language: Английский

Citations

2
Organophotocatalytic Access to C-Glycosides: Multicomponent Coupling Reactions from Glycosyl Bromides DOI

Naoya Sawada,

Ziyi Yu,

Hiryu Takinami

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(66), P. 8684 - 8687

Published: Jan. 1, 2024

Photochemical multi-component coupling reactions initiated by the activation of glycosyl bromides in presence 1,4-bis(diphenylamino)benzene (BDB) as an organic photocatalyst were developed.

Language: Английский

Citations

1
Rh(III)-Catalyzed, Redox-Neutral, C–H Multifluoroalkenylation of Benzamides DOI
Wen‐Hua Chen, Jun Xu, Jia‐Qiang Wu

et al.

Synthesis, Journal Year: 2024, Volume and Issue: 56(19), P. 3045 - 3053

Published: June 11, 2024

Abstract Fluorinated molecules are widely used in pharmaceutical and agrochemical industries. Multifluoroalkyl-containing compounds have attracted increasing attention for their unique ability to alter the activity of drugs bioactive molecules. Herein, we report an efficient Rh(III)-catalyzed, redox-neutral, C–H multifluoroalkenylation benzamides with multifluoroalkenes, which provides a versatile protocol accessing wide range multifluoroalkenylated arenes.

Language: Английский

Citations

0
Modular Assembly of Acridines by Integrating Photo‐Excitation of o‐Alkyl Nitroarenes with Copper‐Promoted Cascade Annulation DOI

Haichao Huang,

Yi‐Fan Jiang,

Wei Yuan

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: July 23, 2024

Abstract Acridine frameworks stand as pivotal architectural elements in pharmaceuticals and photocatalytic applications, owing to their chemical adaptability, biological activity, unique excited‐state dynamics. Conventional synthetic routes often entail specialized starting materials, anaerobic or moisture‐free conditions, elaborate multi‐stage manipulations for incorporating diverse functionalities. Herein, we present a convergent approach integrating photo‐excitation of readily available ortho ‐alkyl nitroarenes with copper‐promoted cascade annulation. This innovative system enables an aerobic, one‐pot reaction o‐ alkyl arylboronic acids, thereby streamlining the modular construction wide array acridine derivatives various functional groups. encompasses symmetrical, unsymmetrical polysubstituted varieties, some which are otherwise exceptionally difficult synthesize. Furthermore, it significantly improves production structurally varied acridinium salts, featuring enhanced photophysical properties, high excited state potentials ( E * red =2.08–3.15 V), exhibiting superior performance intricate photoredox transformations.

Language: Английский

Citations

0
Modular Assembly of Acridines by Integrating Photo‐Excitation of o‐Alkyl Nitroarenes with Copper‐Promoted Cascade Annulation DOI

Haichao Huang,

Yi‐Fan Jiang,

Wei Yuan

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(42)

Published: July 23, 2024

Abstract Acridine frameworks stand as pivotal architectural elements in pharmaceuticals and photocatalytic applications, owing to their chemical adaptability, biological activity, unique excited‐state dynamics. Conventional synthetic routes often entail specialized starting materials, anaerobic or moisture‐free conditions, elaborate multi‐stage manipulations for incorporating diverse functionalities. Herein, we present a convergent approach integrating photo‐excitation of readily available ortho ‐alkyl nitroarenes with copper‐promoted cascade annulation. This innovative system enables an aerobic, one‐pot reaction o‐ alkyl arylboronic acids, thereby streamlining the modular construction wide array acridine derivatives various functional groups. encompasses symmetrical, unsymmetrical polysubstituted varieties, some which are otherwise exceptionally difficult synthesize. Furthermore, it significantly improves production structurally varied acridinium salts, featuring enhanced photophysical properties, high excited state potentials ( E * red =2.08–3.15 V), exhibiting superior performance intricate photoredox transformations.

Language: Английский

Citations

0
Photoredox-catalyzed intramolecular nucleophilic amidation of alkenes with β-lactams DOI Creative Commons
Valentina Giraldi, Giandomenico Magagnano, Daria Giacomini

et al.

Beilstein Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 20, P. 2461 - 2468

Published: Oct. 1, 2024

The direct nucleophilic addition of amides to unfunctionalized alkenes via photoredox catalysis represents a facile approach towards functionalized alkylamides. Unfortunately, the scarce nucleophilicity and competitive side reactions limit utility this approach. Herein, we report an intramolecular cyclization with β-lactams in presence acridinium photocatalyst. uses β-lactam nitrogen atom radical cation photogenerated linked alkene moiety, followed by hydrogen transfer from (HAT) catalyst. This process was used successfully prepare 2-alkylated clavam derivatives.

Language: Английский

Citations

0
Reassessing the Photochemical Upcycling of Polystyrene Using Acridinium Salts DOI Creative Commons

Anne‐Lise De Abreu,

Daniel Taton, Dario M. Bassani

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 13, 2024

Abstract Polystyrene ( PS ) is a commodity plastic recalcitrant to chemical recycling or upcycling processes. Approaches aimed at deconstructing by photocatalytic means struggle generate high‐energy species capable of cleaving the robust C−H and C−C bonds . We show that 9‐mesityl‐10‐methylacridinium perchlorate MA various grades substrates into up 40 % benzoic acid BAc ), formic FA small proportions acetophenone ACP under visible light (456 nm) through solar radiation. Time‐resolved emission absorption spectroscopy evidence reaction with oxygen primary photochemical step in oxygen‐saturated solutions, accounting for 77 photons absorbed vs. 1 direct (0.303 M repeating units). These results are agreement mechanism which ‐mediated photo occurs abstraction benzylic H atoms reactive generated energy electron transfer from excited state Addition triplet O 2 these radicals, followed intra‐ inter‐molecular hydrogen atom (HAT) generates C‐ O‐centered radicals then undergoing β‐scission hydroperoxide fragmentation. The formation intermediate oligomers functionalized terminal carbonyl groups demonstrated both infrared analysis MALDI TOF mass spectrometry. undergo further photoinduced conversion even absence , as evidenced size exclusion chromatography irradiated samples.

Language: Английский

Citations

0
Reassessing the Photochemical Upcycling of Polystyrene Using Acridinium Salts DOI Creative Commons
Ana S. Abreu, Daniel Taton, Dario M. Bassani

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 13, 2024

Abstract Polystyrene ( PS ) is a commodity plastic recalcitrant to chemical recycling or upcycling processes. Approaches aimed at deconstructing by photocatalytic means struggle generate high‐energy species capable of cleaving the robust C−H and C−C bonds . We show that 9‐mesityl‐10‐methylacridinium perchlorate MA various grades substrates into up 40 % benzoic acid BAc ), formic FA small proportions acetophenone ACP under visible light (456 nm) through solar radiation. Time‐resolved emission absorption spectroscopy evidence reaction with oxygen primary photochemical step in oxygen‐saturated solutions, accounting for 77 photons absorbed vs. 1 direct (0.303 M repeating units). These results are agreement mechanism which ‐mediated photo occurs abstraction benzylic H atoms reactive generated energy electron transfer from excited state Addition triplet O 2 these radicals, followed intra‐ inter‐molecular hydrogen atom (HAT) generates C‐ O‐centered radicals then undergoing β‐scission hydroperoxide fragmentation. The formation intermediate oligomers functionalized terminal carbonyl groups demonstrated both infrared analysis MALDI TOF mass spectrometry. undergo further photoinduced conversion even absence , as evidenced size exclusion chromatography irradiated samples.

Language: Английский

Citations

0