Multimodal Acridine Photocatalysis Enables Direct Access to Thiols from Carboxylic Acids and Elemental Sulfur DOI

Arka Porey,

Seth O. Fremin, Sachchida Nand

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(9), P. 6973 - 6980

Published: April 19, 2024

Development of photocatalytic systems that facilitate mechanistically divergent steps in complex catalytic manifolds by distinct activation modes can enable previously inaccessible synthetic transformations. However, multimodal remain understudied, impeding their implementation methodology. We report herein a access to thiols directly merges the structural diversity carboxylic acids with ready availability elemental sulfur without substrate preactivation. The transformation provides direct radical-mediated segue one most biologically important and synthetically versatile organosulfur functionalities, whose accessibility remains largely dominated two-electron-mediated processes based on toxic uneconomical reagents precursors. two-phase radical process is facilitated reactivity acridine photocatalysis enables both singlet excited state PCET-mediated decarboxylative carbon–sulfur bond formation unknown reductive disulfur cleavage photoinduced hydrogen atom transfer silane–triplet system. study points significant potential providing unexplored directions

Language: Английский

Photoredox-Enabled Dearomative [2π + 2σ] Cycloaddition of Phenols DOI
Subhabrata Dutta, Donghyeon Lee,

Kristers Ozols

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(4), P. 2789 - 2797

Published: Jan. 18, 2024

Dearomative photocycloaddition of monocyclic arenes is an appealing strategy for comprehending the concept "escape from flatland". This brings replacement readily available planar aromatic hydrocarbon units with a 3D fused bicyclic core sp3-enriched carbon units. Herein, we outline intermolecular approach dearomative phenols. In order to circumvent ground-state aromaticity and construct conformationally restrained building blocks, bicyclo[1.1.0]butanes were chosen as coupling partners. renders straightforward access bicyclo[2.1.1]hexane unit cyclic enone moiety, which further contributed synthetic linchpin postmodifications. Mechanistic experiment advocates plausible onset both reactants, depending on redox potential.

Language: Английский

Citations

66
Double Strain-Release [2π+2σ]-Photocycloaddition DOI
Subhabrata Dutta, Yilin Lu, Johannes E. Erchinger

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(8), P. 5232 - 5241

Published: Feb. 13, 2024

In pursuit of potent pharmaceutical candidates and to further improve their chemical traits, small ring systems can serve as a potential starting point. Small units have the additional merit loaded strain at core, making them suitable reactants they capitalize on this intrinsic driving force. With introduction cyclobutenone strained precursor ketene, photocycloaddition with another unit, bicyclo[1.1.0]butane (BCB), enables reactivity both π-units in transient ketene. This double strain-release driven [2π+2σ]-photocycloaddition promotes synthesis diverse heterobicyclo[2.1.1]hexane units, pharmaceutically relevant bioisostere. The effective under catalyst-free conditions high functional group tolerance defines its synthetic utility. Experimental mechanistic studies density theory (DFT) calculations suggest that takes place via triplet mechanism.

Language: Английский

Citations

43
Recent advances in oxidative degradation of plastics DOI Creative Commons
Sewon Oh, Erin E. Stache

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(14), P. 7309 - 7327

Published: Jan. 1, 2024

Oxidative degradation is a powerful method to degrade plastics into oligomers and small oxidized products. While thermal energy has been conventionally employed as an external stimulus, recent advances in photochemistry have enabled photocatalytic oxidative of polymers under mild conditions. This tutorial review presents overview degradation, from its earliest examples emerging strategies. briefly discusses the motivation development with focus on underlying mechanisms. Then, we will examine modern studies primarily relevant catalytic degradation. Lastly, highlight some unique using unconventional approaches for polymer such electrochemistry.

Language: Английский

Citations

32
Synthesis of Borylated Carbocycles by [2 + 2]-Cycloadditions and Photo-Ene Reactions DOI
Jarett M. Posz,

Neetu Sharma,

Paige A. Royalty

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(14), P. 10142 - 10149

Published: March 27, 2024

Saturated bicyclic compounds make up a valuable class of building blocks in the development agrochemicals and pharmaceuticals. Here, we present synthesis borylated bicyclo[2.1.1]hexanes via crossed [2 + 2]-cycloaddition. Due to presence C–B bond, variety structures can be easily prepared that are not accessible by other methods. Moreover, rare photo-ene reaction is also disclosed, allowing for diastereoselective trisubstituted cyclopentanes.

Language: Английский

Citations

28
γ-Amino Alcohols via Energy Transfer Enabled Brook Rearrangement DOI Creative Commons
Ranjini Laskar, Subhabrata Dutta, Jan C. Spies

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(15), P. 10899 - 10907

Published: April 3, 2024

In the long-standing quest to synthesize fundamental building blocks with key functional group motifs, photochemistry in recent past has comprehensively established its attractiveness. Amino alcohols are not only functionally diverse but ubiquitous biologically active realm of compounds. We developed bench-stable bifunctional reagents that could then access sparsely reported γ-amino directly from feedstock alkenes through energy transfer (EnT) photocatalysis. A designed 1,3-linkage across is made possible by intervention a radical Brook rearrangement takes place downstream EnT-mediated homolysis our reagent(s). combination experimental mechanistic investigations and detailed computational studies (DFT) indicates chain propagated reaction pathway.

Language: Английский

Citations

25
Di-π-ethane Rearrangement of Cyano Groups via Energy-Transfer Catalysis DOI
Yu Zheng,

Qi-Xin Dong,

Shu‐Ya Wen

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(27), P. 18210 - 18217

Published: May 24, 2024

Molecular rearrangement occupies a pivotal position among fundamental transformations in synthetic chemistry. Radical translocation has emerged as prevalent tool, efficiently facilitating the migration of diverse functional groups. In contrast, development di-π-methane remains limited, particularly terms cyano This is primarily attributed to energetically unfavorable three-membered-ring transition state. Herein, we introduce an unprecedented di-π-ethane enabled by energy-transfer catalysis under visible light conditions. innovative open-shell boasts broad tolerance toward range groups, encompassing even complex drug and natural product derivatives. Overall, reported represents complementary strategy radical catalysis.

Language: Английский

Citations

24
Challenges and Future Perspectives in Photocatalysis: Conclusions from an Interdisciplinary Workshop DOI Creative Commons
Sebastian B. Beil, Sylvestre Bonnet, Carla Casadevall

et al.

JACS Au, Journal Year: 2024, Volume and Issue: 4(8), P. 2746 - 2766

Published: Aug. 8, 2024

Photocatalysis is a versatile and rapidly developing field with applications spanning artificial photosynthesis, photo-biocatalysis, photoredox catalysis in solution or supramolecular structures, utilization of abundant metals organocatalysts, sustainable synthesis, plastic degradation. In this Perspective, we summarize conclusions from an interdisciplinary workshop young principal investigators held at the Lorentz Center Leiden March 2023. We explore how diverse fields within photocatalysis can benefit one another. delve into intricate interplay between these subdisciplines, by highlighting unique challenges opportunities presented each multidisciplinary approach drive innovation lead to solutions for future. Advanced collaboration knowledge exchange across domains further enhance potential photocatalysis. Artificial photosynthesis has become promising technology solar fuel generation, instance, via water splitting CO

Language: Английский

Citations

22
A General Approach for the Synthesis of Cyanoisopropyl Bicyclo[1.1.1]pentane (BCP) Motifs by Energy Transfer Process DOI
Lin Li, Qing Pang, Binbin Chen

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(33), P. 7060 - 7065

Published: Aug. 13, 2024

Bicyclo[1.1.1]pentane (BCP) heteroaryls make up an important class of BCP derivatives in drug discovery. Herein, we report the visible-light-mediated synthesis cyanoisopropyl BCP-heteroaryls motifs from

Language: Английский

Citations

19
Merging Photoinduced Electron Transfer with Hydrogen Atom Transfer: Formal β-C(sp3)–H Pyridination of Carbonyls DOI
Jian Li, Jun Xu, Binbin Chen

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 9, 2025

In this study, a novel approach that combines photoinduced electron transfer (ET) with hydrogen atom (HAT) has been introduced for the selective β-C(sp3)–H pyridination of carbonyl compounds. This method is notable its absence transition metals and ability to function under benign reaction conditions, resulting in range pyridinated derivatives consistently moderate good yields. The significance technique further underscored by potential late-stage functionalization pharmaceutically significant molecules. Mechanistic investigations confirmed proceeds via radical-mediated pathway.

Language: Английский

Citations

5
Visible-Light-Induced Energy-Transfer-Mediated Hydrofunctionalization and Difunctionalization of Unsaturated Compounds via Sigma-Bond Homolysis of Energy-Transfer Acceptors DOI
Qiao Sun, Shaopeng Wang, Yuan Xu

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 1854 - 1941

Published: Jan. 17, 2025

Over the past decade, visible-light-mediated energy-transfer (EnT) catalysis, particularly triplet–triplet (TTEnT) has emerged as a mild and environmentally friendly approach for diverse organic synthetic transformations. In contrast to photoredox which typically requires sacrificial electron donors or acceptors complete catalytic cycle, EnT photocatalysis generally proceeds with high atom economy while minimizing generation of wasteful byproducts. Furthermore, successful catalysis is contingent upon precise control redox potentials both photocatalysts substrates, strategies are primarily influenced by triplet energy compatibility between these entities. Considering growing importance photocatalysis, well hydrofunctionalization difunctionalization reactions in synthesis, this review systematically summarizes significant advancements EnT-enabled unsaturated compounds via sigma-bond homolysis over decade. Special emphasis placed on elucidating substrate scopes mechanistic scenarios. Additionally, discusses versatile applications methodologies addresses current challenges opportunities within evolving research field. This structured into six main categories based different types sigma-bonds undergoing homolysis. These include transformations mediated 1) N–O bond oxime esters other N,O-radical precursors; 2) N–S N-sulfonyl imines N,S-radical 3) chalcogen–chalcogen disulfides oxy/thio/selenosulfonates; 4) C–S tri/difluoromethylated sulfinates, acetylenic triflones, arylsulfonium salts; 5) C–X (X = halogen) halides; 6) acceptors. Through providing theoretical backgrounds along comprehensive overview currently employed acceptors, photosensitizers, contemporary EnT-induced compounds, aims serve an invaluable resource future innovations rapidly

Language: Английский

Citations

5