C─H Functionalization of Heteroarenes via Electron Donor‐Acceptor Complex Photoactivation DOI
Alakananda Hajra,

Madhusudan Mondal,

Sumit Ghosh

et al.

ChemSusChem, Journal Year: 2024, Volume and Issue: unknown

Published: July 8, 2024

C-H Functionalization of heteroarenes stands as a potent instrument in organic synthesis, and with the incorporation visible light, it emerged transformative game-changer. In this domain, electron donor-acceptor (EDA) complex, formed through pairing an electron-rich substrate electron-accepting molecule, has garnered substantial consideration recent years due to related avoidance requirement photocatalyst well oxidant. EDA complexes can undergo photoactivation under mild conditions exhibit high functional group tolerance, making them potentially suitable for functionalization biologically relevant heteroarenes. This review article provides overview advancements field via complex literature coverage up April, 2024.

Language: Английский

Arylthianthrenium Salts as the Aryl Sources: Visible Light/Copper Catalysis-Enabled Intermolecular Azidosulfonylation of Alkenes DOI
Hao Xu, Xufeng Li, Yifei Wang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(9), P. 1845 - 1850

Published: Feb. 26, 2024

The difunctionalization of alkenes using aryl thianthrenium salts as the sources has been reported sporadically. However, four-component on basis not thus far and still remains a challenge. Herein, visible light/copper catalysis-enabled reaction salts, DABCO·(SO

Language: Английский

Citations

23
Synthetic Applications of Sulfonium Salts as Aryl Radical Precursors DOI Open Access

Xinyin Wu,

Pan Gao, Feng Chen

et al.

European Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 26(43)

Published: Sept. 13, 2023

Abstract The utilization of aryl radicals as open‐shelled intermediates has become an essential tool for both conventional and state‐of‐the‐art synthetic chemistry. However, the current methods generating are still inefficient, greatly impeding their practical applications. Encouragingly, sulfonium salts have emerged appealing sources a wide range transformations aimed at creating novel chemical bonds driven by distinctive structural attributes tendencies. This review primarily focuses on specific reaction mechanisms underlying cleavage C−S in salts, leading to generation corresponding within diverse conditions.

Language: Английский

Citations

36
Photocatalyst/metal-free sequential C–N/C–S bond formation: Synthesis of S-arylisothioureas via photoinduced EDA complex activation DOI

Guoju Guo,

Xufeng Li, Jie Ma

et al.

Chinese Chemical Letters, Journal Year: 2024, Volume and Issue: 35(11), P. 110024 - 110024

Published: May 17, 2024

Language: Английский

Citations

15
Photoinduced C(sp3)−H Bicyclopentylation Enabled by an Electron Donor–Acceptor Complex‐Mediated Chemoselective Three‐Component Radical Relay DOI

Xiaobo Dang,

Zhixuan Li,

Jinlong Shang

et al.

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

Published: April 10, 2024

The photoredox electron donor-acceptor (EDA) complex-mediated radical coupling reaction has gained prominence in the field of organic synthesis, finding widespread application two-component reactions. However, EDA complex-promoted multi-component reactions are not well developed with only a limited number examples have been reported. Herein, we report photoinduced and highly chemoselective three-component arylalkylation [1.1.1]propellane, which allows direct functionalization C(sp

Language: Английский

Citations

11
Visible light/copper catalysis enabled Heck-like coupling between alkenes and cyclic sulfonium salts via selective C–S bond cleavage DOI

Xianqin Liu,

Xufeng Li, Linyuan Wang

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(8), P. 2195 - 2200

Published: Jan. 1, 2024

A Heck-like coupling of cyclic sulfonium salts with alkenes via selective C–S bond cleavage using a copper complex as photosensitizer through visible-light-driven redox-neutral process has been developed.

Language: Английский

Citations

9
Electron Donor–Acceptor Complex Enabled Cyclization/Sulfonylation Cascade of N-Heterocycles with Thianthrenium Salts DOI

Zhengjun He,

Zhi Li,

Shuo Lai

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(31), P. 6652 - 6657

Published: July 26, 2024

We report a visible-light-promoted cyclization/sulfonylation cascade of N-heterocycles with thianthrenium salts using DABSO as the SO2 surrogate. This method features excellent functional group tolerance, wide substrate scope, and late-stage elaboration bioactive relevant molecules. Mechanistic investigations reveal that photoactive electron donor–acceptor (EDA) complexes between DABCO are capable generation aryl radicals, which induce following insertion by attacking DABSO, thus triggering key radical cyclization step.

Language: Английский

Citations

7
Site‐Selective S‐Arylation of 1‐Thiosugars with Aryl Thianthrenium Salts through Copper(I)‐Mediated, Photoredox‐ Catalyzed Reactions DOI
Yini Fang,

Qing Liang,

Lingling Shi

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(10), P. 2344 - 2351

Published: April 5, 2024

Abstract A process for the synthesis of aryl thioglycosides from thianthrenium salts and 1‐thiosugars is achieved by copper(I)‐mediated, photoredox‐catalyzed reactions. The desired products could be obtained in 32% to 78% yield after irradiation with 34 W blue light at room temperature. Various functional groups, especially including halogen were well tolerated under standard reaction conditions. This strategy differs conceptually all previous S ‐glycosylations that thiosugar functionality incorporated into complex natural or drugs a late stage site‐selectively, which has not been shown via halides aryldiazonium salts.

Language: Английский

Citations

6
Site-selective and metal-free C–H phosphonation of arenes via photoactivation of thianthrenium salts DOI Creative Commons
Albert Gallego‐Gamo, David Reyes-Mesa, Axel Guinart-Guillem

et al.

RSC Advances, Journal Year: 2023, Volume and Issue: 13(33), P. 23359 - 23364

Published: Jan. 1, 2023

Aryl phosphonates are accessed by visible-light irradiation of new EDA complex between thianthrenium salts as electron-acceptors and phosphites electron-donor molecules.

Language: Английский

Citations

14
Site‐Selective Ortho/Ipso C−H Difunctionalizations of Arenes using Thianthrene as a Leaving Group DOI Creative Commons
Dorian Dupommier, Martin Vuagnat, Javid Rzayev

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(30)

Published: May 7, 2024

Abstract Site‐selective ortho/ipso C−H difunctionalizations of aromatic compounds were designed to afford polyfunctionalized arenes including challenging 1,2,3,4‐tetrasubstituted ones (62 examples, up 97 % yields). To ensure the excellent regioselectivity process while keeping high efficiency, an original strategy based on a “C−H thianthenation/Catellani‐type reaction” sequence was developed starting from simple arenes. Non‐prefunctionalized first regioselectively converted into corresponding thianthrenium salts. Then, palladium‐catalyzed, norbornene (NBE)‐mediated allowed synthesis ipso ‐olefinated/ ortho ‐alkylated using thianthrene as leaving group (revisited Catellani reaction). Pleasingly, commercially available (NBE) and unique catalytic system, synthetic challenges known for reaction with aryl iodides smoothly successfully tackled “thianthrenium” approach. The protocol robust (gram‐scale reaction) widely applied two‐fold functionalization various bio‐active compounds. Moreover, panel olefins alkyl halides coupling partners suitable. further incorporation other groups at (CN/alkyl/H, aryl) (alkyl, aryl, amine, thiol) positions, showcasing generality process.

Language: Английский

Citations

5
Ring-Opening Sulfonylation of Cyclic Sulfonium Salts with Sodium Sulfinates under Transition-Metal- and Additive-Free Conditions DOI
Lihua Yang,

Xiangda Liu Xiangda Liu,

Chu Liu

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(17), P. 12668 - 12680

Published: Aug. 9, 2024

Incorporating a sulfonyl group into parent molecules has been shown to effectively improve their synthetic applications and bioactivities. In this study, we present straightforward practical approach for the ring-opening reaction of alkenyl–aryl sulfonium salts with sodium sulfinates produce range sulfur-containing alkyl sulfones. This method offers benefits mild conditions, easily accessible raw materials, wide substrate applicability, good functional compatibility, operational simplicity. Importantly, resulting products can be readily converted sulfoxides, sulfones, sulfoximines, some heterocyclic compounds.

Language: Английский

Citations

5