Thiols as Powerful Atom Transfer Catalyst: Opportunities in Photoredox‐Mediated Reactions DOI
Xiaobo Bao,

Wei Yu,

Guoli Wang

et al.

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(14), P. 2299 - 2309

Published: June 12, 2023

Abstract The employing visible light to drive organic transformations is the most promising choice meet needs for green synthesis, in which reactions promoted by may provide a more efficient and greener method. Currently, abundant methods activation functionalization of reaction substrates have relied on direct single‐electron transfer (SET) between excited photocatalyst substrates, these wonderful works were summarized docoumented many reviews. As complement above reactions, photoredox‐mediated atom (photocatalyst‐to‐HAT catalyst‐to‐substrates) generate radical species are showing an explosively growing trend. In this review, we highlight recent significant developments rapidly area, mainly focusing photoinduced base‐to‐substrates charge reactions.

Language: Английский

Sulfonium Salts as Acceptors in Electron Donor‐Acceptor Complexes DOI Creative Commons
Leendert van Dalsen,

Rachel E. Brown,

James A. Rossi‐Ashton

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(29)

Published: March 24, 2023

Abstract The photoactivation of electron donor‐acceptor complexes has emerged as a sustainable, selective and versatile strategy for the generation radical species. Electron (EDA) complexation, however, imposes electronic constraints on donor acceptor components this can limit range radicals that be generated using approach. New EDA complexation strategies exploiting sulfonium salts allow to from native functionality. For example, aryl salts, formed by activation arenes, serve in due their electron‐deficient nature. This “sulfonium tag” approach relaxes parent substrate dramatically expands complexation. In review, these new applications will introduced areas chemical space rendered accessible through innovation highlighted.

Language: Английский

Citations

98
EDA photochemistry: Mechanistic investigations and future opportunities DOI Creative Commons
Alan Wortman, Corey R. J. Stephenson

Chem, Journal Year: 2023, Volume and Issue: 9(9), P. 2390 - 2415

Published: July 18, 2023

Language: Английский

Citations

82
An electron donor–acceptor photoactivation strategy for the synthesis of S-aryl dithiocarbamates using thianthrenium salts under mild aqueous micellar conditions DOI
Hao Xu, Xufeng Li, Jie Ma

et al.

Chinese Chemical Letters, Journal Year: 2023, Volume and Issue: 34(11), P. 108403 - 108403

Published: March 30, 2023

Language: Английский

Citations

52
Recent Advances in Electron Donor‐Acceptor (EDA)‐Complex Reactions involving Quaternary Pyridinium Derivatives DOI

Barakha Saxena,

Roshan I. Patel,

Anuj Sharma

et al.

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(10), P. 1538 - 1564

Published: March 6, 2023

Abstract Quaternary pyridinium compounds are valuable intermediates in organic synthesis, which have gained immense popularity the synthetic community. The application of transition metal or photoredox catalysis transforming quaternary into various C−C and C−X bonds is well established. A majority these methods require high temperatures, expansive catalysts, delicate conditions for successful execution. On other hand, use metal‐free photocatalysis‐free strategies constructing using derivatives has been sought‐after. In this context, electron‐donor‐acceptor (EDA)‐complex reactions emerged as a state‐of‐the‐art methodology, do not any photocatalyst their EDA‐complex photochemistry takes advantage electron‐acceptor ability derivatives, can quickly generate radical precursor via deaminative process. These newly generated useful several transformations. We hereby, review, discuss an area major progress mediated involving with mechanism, substrate scope, limitations. magnified image

Language: Английский

Citations

48
Characterization of A π–π stacking cocrystal of 4-nitrophthalonitrile directed toward application in photocatalysis DOI Creative Commons
Ting Xue, Cheng Ma, Le Liu

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Feb. 16, 2024

Abstract Photoexcitation of the electron-donor-acceptor complexes have been an effective approach to achieve radicals by triggering electron transfer. However, catalytic version complex photoactivation is quite underdeveloped comparing well-established utilization electronically biased partners. In this work, we utilize 4-nitrophthalonitrile as acceptor facilitate efficient π-stacking with electron-rich aromatics form complex. The characterization and energy profiles on cocrystal 1,3,5-trimethoxybenzene disclose that transfer highly favorable under light irradiation. This catalyst can be efficiently applied in benzylic C−H bond developing Giese reaction alkylanisoles oxidation benzyl alcohols. A broad scope tolerated a mechanism also proposed. Moreover, corresponding π-anion interaction potassium formate further hydrocarboxylation alkenes efficiently.

Language: Английский

Citations

19
Thianthrenium-Enabled Phosphorylation of Aryl C–H Bonds via Electron Donor–Acceptor Complex Photoactivation DOI
Hao Xu, Xufeng Li,

Yuzheng Dong

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(20), P. 3784 - 3789

Published: May 16, 2023

An efficient strategy for the preparation of aryl phosphonates via blue-light-promoted single electron transfer process an EDA complex between phosphites and thianthrenium salts has been demonstrated. The corresponding substituted were obtained in good to excellent yields, byproduct thianthrene can be recovered reused quantity. This developed method realizes construction through indirect C-H functionalization arenes, which potential application value drug discovery development.

Language: Английский

Citations

43
Radical Perfluoroalkylation of Aliphatic Substrates DOI
Damian E. Yerien, Sebastián Barata‐Vallejo, Al Postigo

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(12), P. 7756 - 7794

Published: May 25, 2023

A selection of perfluoroalkylation reactions aliphatic substrates that display methodological and synthetic amplitude will be studied, giving examples their applications mechanistic details. An array approaches for fluoroalkylation are documented; in particular, radical protocols prominent among methods. To effect, addition perfluoroalkyl radicals RF (RF=CnF2n+1, n > 1) to unsaturated organic serve as one the most direct efficacious ways access fluoroalkylated scaffolds. The syntheses perfluoroalkyl-substituted vinyl, alkynyl, allylic compounds; hydro-, iodo-, oxy-perfluoroalkylated alkanes olefins; carbonyl enamides, amides, thioamides, hydrazones; multicomponent studied. While there a number accomplished reports on organofluorination, we aim provide an overview radical-involved substrates, covering from 2018 early 2023, summarized Tables 1–4.

Language: Английский

Citations

41
Synthesis of 1-perfluoroalkyl-3-heteroaryl bicyclo[1.1.1]pentanes via visible light-induced and metal-free perfluoroalkylation of [1.1.1]propellane DOI

Boan Yan,

Gongcheng Xu,

Hang Han

et al.

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(5), P. 1948 - 1954

Published: Jan. 1, 2023

Visible light-induced perfluoroalkylation of [1.1.1]propellane provides a sustainable way to incorporate perfluoroalkyl-substituted BCPs into various heterocycles.

Language: Английский

Citations

38
Photosynthesis of 3-Alkylated Coumarins from Carboxylic Acids Catalyzed by a Na2S-Based Electron Donor–Acceptor Complex DOI

Hai‐Yang Song,

Meiyi Liu,

Jing Huang

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(4), P. 2288 - 2295

Published: Feb. 4, 2023

A simple and practical electron donor-acceptor (EDA) strategy to synthesize various 3-alkylated coumarins from easily available naturally abundant carboxylic acids under photocatalyst-, oxidant-, additive-free mild conditions is reported. Using Na2S as the catalytic donor, a series of primary, secondary, tertiary carbon radicals can be efficiently generated, EDA complex regenerated without an alkaline additive.

Language: Английский

Citations

32
Triarylamines as catalytic donors in light-mediated electron donor–acceptor complexes DOI Creative Commons
Durbis J. Castillo‐Pazos, Juan D. Lasso, Ehsan Hamzehpoor

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(13), P. 3470 - 3481

Published: Jan. 1, 2023

Recently, photochemistry of Electron Donor-Acceptor (EDA) complexes employing catalytic amounts electron donors have become interest as a new methodology in the catalysis field, allowing for decoupling transfer (ET) from bond-forming event. However, examples practical EDA systems regime remain scarce, and their mechanism is not yet well-understood. Herein, we report discovery an complex between triarylamines α-perfluorosulfonylpropiophenone reagents, catalyzing C-H perfluoroalkylation arenes heteroarenes under visible light irradiation pH- redox-neutral conditions. We elucidate this reaction using detailed photophysical characterization complex, resulting triarylamine radical cation, its turnover

Language: Английский

Citations

31