Nickel-Catalyzed Gas-Free Reductive Carbonylation of Aryl Thianthrenium Salts to Access Aryl Amides and Aryl Thioesters DOI
Chen Chen,

Luyao Ding,

Xiaoxu Zhang

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: May 1, 2025

A nickel-catalyzed site-selective reductive carbonylation of arenes via aryl thianthrenium salts is described. Using Mo(CO)6 as a convenient solid CO source and reductant employing nitroarenes sulfonyl chlorides readily available nitrogen sulfur sources, range amides thioesters were successfully synthesized in moderate to good yields. The utility this transformation demonstrated through the synthesis antimicrobial agents late-stage functionalization biorelevant molecules.

Language: Английский

C–heteroatom coupling with electron-rich aryls enabled by nickel catalysis and light DOI Creative Commons
Shengyang Ni, Riya Halder, Dilgam Ahmadli

et al.

Nature Catalysis, Journal Year: 2024, Volume and Issue: 7(6), P. 733 - 741

Published: May 7, 2024

Abstract Nickel photoredox catalysis has resulted in a rich development of transition-metal-catalysed transformations for carbon–heteroatom bond formation. By harnessing light energy, the transition metal can attain oxidation states that are difficult to achieve through thermal chemistry catalytic manifold. For example, nickel reactions have been reported both synthesis anilines and aryl ethers from aryl(pseudo)halides. However, oxidative addition simple systems is often sluggish absence special, electron-rich ligands, leading catalyst decomposition. Electron-rich electrophiles therefore currently fall outside scope many field. Here we provide conceptual solution this problem demonstrate nickel-catalysed C–heteroatom bond-forming arylthianthrenium salts, including amination, oxygenation, sulfuration halogenation. Because redox properties salts primarily dictated by thianthrenium, highly donors be unlocked using NiCl 2 under irradiation form desired C‒heteroatom bonds.

Language: Английский

Citations

21
Standardized Approach for Diversification of Complex Small Molecules via Aryl Thianthrenium Salts DOI Creative Commons
Dilgam Ahmadli, Sven Müller, Yuanhao Xie

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 21, 2025

Thianthrenation is a useful strategy for the late-stage diversification of complex small molecules owing to positional selectivity and synthetic versatility thianthrenium salts as electrophilic linchpins. However, substrate-dependent identification suitable reaction conditions thianthrenation can be difficult. Reported functionalization vary significantly and, in some instances, lack robustness practicality. Herein, we report generalized approach preparation two manifolds practical, robust, parallel salts.

Language: Английский

Citations

2
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

38
Photocatalytic Functionalization of Dehydroalanine‐Derived Peptides in Batch and Flow DOI Creative Commons
Nikolaos Kaplaneris, Merve Akdeniz, Méritxell Fillols

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(19)

Published: March 18, 2024

Abstract Unnatural amino acids, and their synthesis by the late‐stage functionalization (LSF) of peptides, play a crucial role in areas such as drug design discovery. Historically, LSF biomolecules has predominantly utilized traditional synthetic methodologies that exploit nucleophilic residues, cysteine, lysine or tyrosine. Herein, we present photocatalytic hydroarylation process targeting electrophilic residue dehydroalanine (Dha). This possesses an α , β ‐unsaturated moiety can be combined with various arylthianthrenium salts, both batch flow reactors. Notably, setup proved instrumental for efficient scale‐up, paving way unnatural acids peptides substantial quantities. Our approach, being inherently mild, permits diversification even when they contain sensitive functional groups. The readily available salts facilitate seamless integration Dha‐containing wide range arenes, blueprints, natural products, culminating creation unconventional phenylalanine derivatives. synergistic effect high group tolerance modular characteristic aryl electrophile enables peptide conjugation ligation conditions.

Language: Английский

Citations

16
Reductive Radical-Polar Crossover Enabled Carboxylative Alkylation of Aryl Thianthrenium Salts with CO2 and Styrenes DOI

Weiguan Qi,

Shiyu Gu,

Lan‐Gui Xie

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(3), P. 728 - 733

Published: Jan. 12, 2024

Carboxylic functionalities are among the pivotal groups in bioactive molecules and synthesis of new lead compounds because their unique character formation hydrogen bonds possibility constructing molecular complexes via amide couplings. We adopt reductive radical-polar crossover strategy to introduce carboxyalkyl into arenes with styrenes CO2 thianthrenium salts. This protocol exhibits excellent potential as a straightforward modular platform for site-selective carboxylative derivation molecules.

Language: Английский

Citations

12
Single-Electron-Transfer-Generated Aryl Sulfonyl Ammonium Salt: Metal-Free Photoredox-Catalyzed Modular Construction of Sulfonamides DOI
Fengying Yan, Qing Li,

Shanshan Fu

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(7), P. 5227 - 5235

Published: March 21, 2024

Sulfonamides are prominently featured in organic synthesis and medicinal chemistry. Yet, a general synthetic platform for the modular construction of aryl sulfonamides remains elusive. Herein, metal-free photoredox-catalyzed three-component via an sulfonyl ammonium salt intermediate, which was generated situ SET event, has been established. A variety structurally diverse primary, secondary, tertiary were synthesized rapidly from abundant amines or sodium azide under mild conditions. Notably, primary aliphatic amine, challenging Cu-catalyzed protocols, worked well this approach. Moreover, fluoride can be accessed smoothly as well, using potassium hydrogen nucleophile. The potential utility conversion is demonstrated facile three bioactive drug compounds. Preliminary mechanistic studies have revealed that radical key intermediates mechanistically innovative methodology.

Language: Английский

Citations

12
Electrocatalytic Formal C(sp2)−H Alkylations via Nickel‐Catalyzed Cross‐Electrophile Coupling with Versatile Arylsulfonium Salts DOI Creative Commons
Takuya Michiyuki, Simon L. Homölle, Neeraj Kumar Pandit

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(29)

Published: May 2, 2024

Producing sp

Language: Английский

Citations

11
Metallaphotoredox deuteroalkylation utilizing thianthrenium salts DOI Creative Commons

Mengjie Jiao,

Jie Zhang, Minyan Wang

et al.

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

Published: June 13, 2024

Abstract Deuterium labeling compounds play a crucial role in organic and pharmaceutical chemistry. The synthesis of such typically involves deuterated building blocks, allowing for the incorporation deuterium atoms functional groups into target molecule single step. Unfortunately, limited availability synthetic approaches to synthons has impeded progress this field. Here, we present an approach utilizing alkyl-substituted thianthrenium salts that efficiently selectively introduce at α position alkyl chains through pH-dependent HIE process, using D 2 O as source. resulting α-deuterated salts, which bear two atoms, exhibit excellent selectivity electrophilic substitution reactions. Through situ formation isotopically labelled halides, these demonstrate compatibility series metallaphotoredox cross-electrophile coupling with (hetero)aryl, alkenyl, bromides, other salts. Our technique allows wide range substrates, high incorporation, precise control over site insertion within benzyl position, allylic or any chain between, well neighboring heteroatoms. This makes it invaluable synthesizing various deuterium-labeled compounds, especially those significance.

Language: Английский

Citations

9
Visible light-promoted defluorinative alkylation/arylation of α-trifluoromethyl alkenes with thianthrenium salts DOI
Yue Zhang, Jianyou Mao, Zhihong Wang

et al.

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(17), P. 9371 - 9377

Published: Jan. 1, 2024

Defluorinative alkylation and arylation between thianthrenium salts α-trifluoromethyl alkene to afford gem -difluoroolefins by easily recycling thianthrene under visible light irradiation free of metal photocatalyst.

Language: Английский

Citations

9
Synthesis of Nickel(I)–Bromide Complexes via Oxidation and Ligand Displacement: Evaluation of Ligand Effects on Speciation and Reactivity DOI
Samuel H. Newman-Stonebraker, T. Judah Raab, Hootan Roshandel

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(35), P. 19368 - 19377

Published: Aug. 23, 2023

Nickel’s +1 oxidation state has received much interest due to its varied and often enigmatic behavior in increasingly popular catalytic methods. In part, the lack of understanding about NiI results from common synthetic strategies limiting breadth complexes that are accessible for mechanistic study catalyst design. We report an oxidative approach using tribromide salts allows generation a well-defined precursor, [NiI(COD)Br]2, as well several new complexes. Included among them bearing bulky monophosphines, which structure–speciation relationships established reactivity Suzuki–Miyaura coupling (SMC) is investigated. Notably, these routes also allow synthesis monomeric t-Bubpy-bound complexes, not previously been achieved. These react with aryl halides, can enable challenging investigations present opportunities catalysis synthesis.

Language: Английский

Citations

22