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

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

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Mechanochemical Copper-Catalyzed Synthesis of NH-Sulfonimidamides by Oxidative Amination of Primary Sulfinamides

ACS Sustainable Chemistry & Engineering, Journal Year: 2024, Volume and Issue: 12(43), P. 15875 - 15880

Published: Oct. 15, 2024

A mechanochemical copper-catalyzed oxidative amination of primary sulfinamides has been developed, leading to NH-sulfonimidamides in moderate good yields under solvent-free conditions. Air serves as a terminal oxidant without the need for external additives. The obtained products could be readily converted into both acyclic and cyclic sulfonimidamide derivatives. This approach demonstrates considerable ecological benefits compared solvent-based methods.

Language: Английский

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Mechanochemical syntheses of N-acyl sulfinamidines via iron-nitrenoids and their conversions to sulfur(VI) derivatives

Green Synthesis and Catalysis, Journal Year: 2025, Volume and Issue: unknown

Published: April 1, 2025

Language: Английский

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Benzodithiazoles‐Sulfoximines: Preparation, Properties and Reactivities as Radical Perfluoroalkylating Agents

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(14), P. 2392 - 2399

Published: June 30, 2023

Abstract We describe the preparation of S‐perfluoroalkyl benzodithiazole trioxides as radical perfluoroalkylating reagents. Their syntheses were performed on a multi‐gram scale by an oxidative cyclization connecting nitrogen sulfoximine and sulfur atom previously introduced in ortho position this group. The structures properties these new molecules carefully examined X‐Ray diffraction, DFT calculations cyclic voltammetry. These data clearly highlight enhanced reactivity sulfoximines compared to their open analogues. This was confirmed photoredox catalysis experiments that revealed interesting reactivity, most especially for introduction di‐ monofluoroalkyl chains.

Language: Английский

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

Published: Feb. 29, 2024

Development of photocatalytic systems that facilitate mechanistically different 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 HAT silane–triplet system. study points significant potential providing new directions

Language: Английский

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Copper-sulfur interactions leading to the formation of S-containing compounds

Tetrahedron Letters, Journal Year: 2024, Volume and Issue: 143, P. 155112 - 155112

Published: May 17, 2024

Language: Английский

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Cyclic Sulfoximines as Methyl and Perdeuteromethyl Transfer Agents and Their Applications in Photoredox Catalysis

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(51)

Published: Sept. 5, 2024

Benzo[1,3,2]dithiazole-1,1,3-trioxides are bench-stable and easy-to-use reagents. In photoredox catalysis, they generate methyl perdeuteromethyl radicals which can add to a variety of radical acceptors, including olefins, acrylamides, quinoxalinones, isocyanides, enol silanes, N-Ts acrylamide. As byproduct, salt is formed be regenerated the original methylating agent. Flow chemistry provides an option for reaction scale-up further underscoring synthetic usefulness these methylation Mechanistic investigations suggest single-electron transfer (SET) pathway induced by catalysis.

Language: Английский

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Palladium‐Catalyzed Domino Reaction for the Synthesis of 3‐Amino 1,2,4‐Benzothiadiazine 1,1‐Dioxides

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 366(4), P. 717 - 724

Published: Oct. 18, 2023

Abstract A palladium‐catalyzed domino reaction of 2‐azidosulfonamides and isocyanides enables the synthesis 3‐amino‐substituted 1,2,4‐benzothiadiazine 1,1‐dioxides at room temperature. By applying commercially available Pd(dba) 2 in catalyst loadings as low 1.0 mol%, a variety 21 differently substituted H ‐1,2,4‐benzothiadiazine can be prepared within h. Moreover, developed protocol gives access to related 4 heterocycles.

Language: Английский

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Ligand-Free, Copper-Catalyzed Coupling Reaction of Aryl Aluminum Reagents with N-Aryl Thiosuccinimides

Letters in Organic Chemistry, Journal Year: 2024, Volume and Issue: 21(12), P. 1055 - 1063

Published: April 19, 2024

: A highly efficient and simple cross-coupling reaction of N-aryl aluminum reagents with Naryl thiosuccinimides for the synthesis diarylsulide derivatives using CuCl (20 mol%) as a catalyst is reported. Under optimum conditions, coupling between aryl different substituents can be carried out smoothly 18-94% isolated yields diarylsulides. The method avoids use expensive transition metals, such Pd, Ir, or Rh, phosphine ligands, has advantages operation high efficiency. structures all target compounds are confirmed by 1HNMR 13CNMR.

Language: Английский

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Accessing Thiols Directly from Carboxylic Acids and Elemental Sulfur by Multimodal Acridine Photocatalysis

Published: Dec. 18, 2023

The thiol group is one of the most biologically important and synthetically versatile organosulfur functionalities that can serve as a central entry point to wide range other sulfur-containing functional groups. Despite their cross-disciplinary importance, synthetic access thiols largely remains dominated by two-electron-mediated processes based on toxic uneconomical reagents precursors. We report herein photocatalytic for first time merges structural diversity carboxylic acids with ready availability elemental sulfur, whose radical reactivity significantly underexplored. two-phase process facilitated multimodal catalytic acridine photocatalysis enables both PCET-mediated decarboxylative carbon–sulfur bond formation previously unknown reductive disulfur cleavage photoinduced HAT in silane–acridine system.

Language: Английский

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