Arylthianthrenium Salts as the Aryl Sources: Visible Light/Copper Catalysis-Enabled Intermolecular Azidosulfonylation of Alkenes

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

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Generation and Application of Aryl Radicals Under Photoinduced Conditions

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(31)

Published: March 28, 2024

Abstract Photoinduced aryl radical generation is a powerful strategy in organic synthesis that facilitates the formation of diverse carbon‐carbon and carbon‐heteroatom bonds. The synthetic applications photoinduced complex compounds, including natural products, physiologically significant molecules, functional materials, have received immense attention. An overview current developments production methods their uses given this article. A generalized idea how to choose reagents approach for radicals described, along with techniques associated mechanistic insights. Overall, article offers critical assessment results as well selection reaction parameters specific context cascades, cross‐coupling reactions, functionalization, selective C−H functionalization substrates.

Language: Английский

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N-Heterocyclic Nitreniums Can Be Employed as Photoredox Catalysts for the Single-Electron Reduction of Aryl Halides

Organic Letters, Journal Year: 2022, Volume and Issue: 24(25), P. 4598 - 4602

Published: June 16, 2022

N-Heterocyclic nitrenium (NHN) salts, the analogues of N-heterocyclic carbenes, have attracted considerable interest. However, relatively little is known about their catalytic ability beyond Lewis acid catalysis. Herein, we describe that NHNs can serve as electron acceptors for charge transfer complex photoactivations. We showcase that, under blue light irradiation, NHN salts could catalyze generation aryl radicals from halides.

Language: Английский

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Solvent-modulated binding selectivity of reaction substrates to onium-based σ-hole donors

Catalysis Science & Technology, Journal Year: 2023, Volume and Issue: 13(11), P. 3375 - 3385

Published: Jan. 1, 2023

Solvation effects might play the dominant role in catalysis providing an increase or suppression of activity organocatalysts.

Language: Английский

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Base-Promoted Ring-Opening Hydroxylation of Cyclic Sulfonium Salts

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(5), P. 3084 - 3091

Published: Feb. 9, 2024

Herein, we reported a general strategy for the synthesis of sulfur-containing primary alcohol derivatives by base-promoted ring-opening hydroxylation cyclic sulfonium salts. A variety salts were successfully transformed into desired hydroxylated products in moderate to excellent yields with good functional group tolerance. Moreover, one-pot synthesis, scale-up reaction, and late-stage functionalization complex molecules demonstrated practicability this synthetic protocol field chemistry.

Language: Английский

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

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

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Synthesis of Sulfur-Containing Trisubstituted Imidazoles by One-Pot, Multicomponent Reaction via Electron Donor–Acceptor Complex Photoactivation

Organic Letters, Journal Year: 2024, Volume and Issue: 26(17), P. 3541 - 3546

Published: April 24, 2024

Rapid and efficient construction of multifunctionalized skeletons through a one-pot multicompound domino reaction has been recognized as simple practical strategy. Herein, visible-light-enabled three-component isothiocyanates, isocyanides, thianthrenium salt-functionalized arenes is presented, which affords facile approach to sulfur-containing trisubstituted imidazoles in good yields with broad substrate scope excellent functional group tolerance. The byproduct thianthrene recovered quantity, thereby ultimately reducing the production chemical waste. developed methodology potential value for discovery development thioimidazole-based drugs.

Language: Английский

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Weak Interaction Activates Esters: Reconciling Catalytic Activity and Turnover Contradiction by Tailored Chalcogen Bonding

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(19), P. 13296 - 13305

Published: May 2, 2024

The activation of esters by strong Lewis acids via the formation covalent adducts is a classic strategy to give reactivity; however, this approach frequently incurs limited turnover due low efficiency in dissociation catalyst from stable catalyst-product complex. While use some weak interaction catalysts that can easily dissociate any bonding complexes reaction system would solve problem, poor catalytic activity ester be provided these noncovalent forces turn sets up formidable challenge. Herein, we describe and transformation interactions, which provides promising platform reconcile problems. Several tailored chalcogen-bonding were developed for esters, enabling achieving several inherently reactive Diels–Alder reactions as well ring-opening polymerization lactones through chalcogen interactions. This supramolecular catalysis particularly highlighted its capability promote uncommon involving using dienes bearing electron-withdrawing groups coupled α,β-unsaturated dienophiles substrate incorporating competitive basic sites, typical showed efficiency, while representative hydrogen halogen inactive.

Language: Английский

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Arylcyanation of Styrenes by Photoactive Electron Donor–Acceptor Complexes/Copper Catalysis

Organic Letters, Journal Year: 2024, Volume and Issue: 26(37), P. 7949 - 7955

Published: Sept. 11, 2024

A novel electron donor-acceptor (EDA) complex/copper catalysis model has been proposed for the construction of 2,3-diarylpropionitriles under visible light conditions. The developed protocol proceeds via intermolecular charge transfer between photoactive EDA complex dibutamine (DBA), aryl thianthrenium salts, and trimethylsilyl cyanide (TMSCN), followed by a copper catalytic cycle. UV-vis absorption measurements confirm participation complexes as reactive intermediates. This three-component process smoothly in presence pharmaceutically relevant core structures sensitive functional groups, which offers possibility precise editing drug molecules with important scaffolds.

Language: Английский

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Halonium and Chalconium Salt-Catalyzed Schiff Condensation: Kinetics and DFT Insights into Organocatalyst Activity Parameters

Organic & Biomolecular Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Chalconium and halonium salts catalyze Schiff condensation. Kinetic data DFT calculations show that the catalytic activity correlates with maximum electrostatic potential on σ-holes, whereas other factors are less significant.

Language: Английский

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