Aryl Thianthrenium Triflates DOI
Riley A. Roberts, David R. Stuart

Encyclopedia of Reagents for Organic Synthesis, Journal Year: 2024, Volume and Issue: unknown, P. 1 - 6

Published: April 18, 2024

image A [ 195072‐48‐1 ] C 19 H 13 F 3 O S (MW 442.48) InChI = 1S/C18H13S2.CHF3O3S/c1‐2‐8‐14(9‐3‐1)20‐17‐12‐6‐4‐10‐15(17)19‐16‐11‐5‐7‐13‐18(16)20;2‐1(3,4)8(5,6)7/h1‐13H;(H,5,6,7)/q+1;/p‐1 InChiKey ILICKJZOLUIMMN‐UHFFFAOYSA‐M B 2839478‐51‐0 20 14 ClF 4 506.95) 1S/C19H14ClOS2.CHF3O3S/c1‐21‐15‐11‐10‐13(12‐14(15)20)23‐18‐8‐4‐2‐6‐16(18)22‐17‐7‐3‐5‐9‐19(17)23;2‐1(3,4)8(5,6)7/h2‐12H,1H3;(H,5,6,7)/q+1;/p‐1 UHXRBIHFIKXURP‐UHFFFAOYSA‐M 2786722‐96‐9 12 6 510.48) 1S/C19H12F3S2.CHF3O3S/c20‐19(21,22)13‐9‐11‐14(12‐10‐13)24‐17‐7‐3‐1‐5‐15(17)23‐16‐6‐2‐4‐8‐18(16)24;2‐1(3,4)8(5,6)7/h1‐12H;(H,5,6,7)/q+1;/p‐1 UEAVFAKSNUECER‐UHFFFAOYSA‐M D 2786723‐55‐3 18 NO 443.47) 1S/C17H12NS2.CHF3O3S/c1‐3‐7‐16‐14(5‐1)19‐15‐6‐2‐4‐8‐17(15)20(16)13‐9‐11‐18‐12‐10‐13;2‐1(3,4)8(5,6)7/h1‐12H;(H,5,6,7)/q+1;/p‐1 SRMXRMTYQFMLCQ‐UHFFFAOYSA‐M (reagents used as an aryl pseudohalide in transition‐metal catalyzed, transition metal‐free, and photochemical reactions) Physical Data : mp 202.8–204.7 °C. 1 159.2–162.7 2 (Not reported). A–D Solubility soluble acetonitrile dichloromethane. – Form Supplied not commercially available; free‐flowing solids prepared by literature procedures. 3–5 Analysis of Reagent Purity NMR. Purification trituration from dichloromethane using diethyl ether or hexanes; silica gel chromatography (eluting with DCM:MeOH). Handling, Storage, Precautions stable under ambient conditions for extended periods time. Can be weighed normal atmosphere stored a vial air. Preparative Methods (From simple arenes) Treatment thianthrene ‐oxide (TTSO) trifluoroacetic anhydride (TFAA) triflic acid (TfOH) the presence desired arene at 0 After addition all reagents, reactions are typically allowed to stir between h depending on substrate. Alternatively, treatment TTSO (Tf O) −40 3,5 completion, purple reaction is quenched methanol generate colorless/yellow solution. The crude mixture concentrated reduced pressure residue triturated afford solid which isolated filtration. arylboronic acids) thianthrene, copper(II) triflate water nitrogen 100 °C h. aqueous workup,

Language: Английский

Organothianthrenium salts: synthesis and utilization DOI Creative Commons
Huan Meng, Ming‐Shang Liu, Wei Shu

et al.

Chemical Science, Journal Year: 2022, Volume and Issue: 13(46), P. 13690 - 13707

Published: Jan. 1, 2022

This review summarizes the synthesis of diverse organothianthrenium salts from various precursors and their applications in organic to forge new C–C, C–H C–heteroatom bonds by C–S bond cleavage with different mechanistic considerations.

Language: Английский

Citations

133
Selective Fluorosulfonylation of Thianthrenium Salts Enabled by Electrochemistry DOI
Xianqiang Kong, Yiyi Chen, Qianwen Liu

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(4), P. 581 - 586

Published: Jan. 25, 2023

A practical electrochemically driven method for fluorosulfonylation of both aryl and alkyl thianthrenium salts has been disclosed. The strategy does not need external redox reagents or metal catalysts. In combination with C-H thianthrenation aromatics, this provides a new tool the site-selective drugs.

Language: Английский

Citations

45
A Practical and Regioselective Strategy for Aromatic C–H Difunctionalization via Site-Selective C–H Thianthrenation DOI
Zhe Zhang, Xi Chen,

Zhi‐Jie Niu

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(9), P. 1813 - 1818

Published: Feb. 22, 2024

Herein, we present a novel Catellani-type reaction that employed aryl-thianthrenium salts as aryl substrates to trigger the subsequent palladium/norbornene cooperatively catalyzed progress. This strategy can achieve site-selective C–H difunctionalization of compounds without directing groups or known initiating reagent. A series functionalized syntheses bioactive molecules further demonstrated potential this strategy.

Language: Английский

Citations

22
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

4
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

17
Site-selective carbonylation of arenes via C(sp2)-H thianthrenation: Palladium-catalyzed direct access to α,β-unsaturated ketones DOI
Jiajun Zhang,

Le‐Cheng Wang,

Yuanrui Wang

et al.

Journal of Catalysis, Journal Year: 2024, Volume and Issue: 432, P. 115454 - 115454

Published: March 20, 2024

Language: Английский

Citations

11
Pd-Catalyzed Decarboxylative Negishi Coupling of Zinc Aryl Carboxylates with Arylthianthrenium Salts DOI
Chun Zhang,

Yangbo Cui,

Xiaoyu Zhou

et al.

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

Published: Feb. 26, 2025

We report a Pd-catalyzed decarboxylative Negishi coupling reaction for efficient biaryl synthesis from various zinc aryl carboxylates, including polyfluorobenzoates and heteroaryl using DMF as the solvent. This mild exhibits broad substrate scope enables late-stage functionalization of bioactive molecules. Mechanistic studies show that DMF-assisted catalyzes decarboxylation polyfluorinated carboxylates to generate arylzinc reagents in situ, which then undergo catalyzed by palladium with arylthianthrenium salts form compounds. Notably, this protocol represents rare example zinc-mediated demonstrates novel strategy preparing easily accessible (hetero)aryl carboxylic acids.

Language: Английский

Citations

1
Palladium-Catalyzed Domino Conversion of Aryl–Thianthreniums with Anhydrides: Rapidly Building Highly Functionalized Fluorenones DOI
Jiang Nan, Haiyan Xiao, Yangmin Ma

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(16), P. 3332 - 3337

Published: April 15, 2024

As a class of rising electrophilic coupling reagents, aryl–thianthreniums (aryl-TTs) have been gaining immense attention. Herein, novel palladium-catalyzed domino annulation aryl-TTs with anhydrides is proposed to rapidly assemble collection highly functionalized fluorenones. This finding presents an innovative reaction pattern wherein the version first involved. Heavily compared existing conversions aryl-TTs, this identified process successively functions as four aryl C–H bonds.

Language: Английский

Citations

9
Catalytic ortho C–H methylation and trideuteromethylation of arylthianthrenium salts via the Catellani strategy DOI
Chen Chen,

Xiaoxu Zhang,

Ziyi Wang

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(12), P. 3333 - 3340

Published: Jan. 1, 2024

We report a Pd/NBE cooperative catalyzed ortho C–H methylation and trideuteromethylation of arylthianthrenium salts, enabling the efficient synthesis wide variety (trideutero)methylated arenes in moderate to good yields.

Language: Английский

Citations

9
Organohypervalent heterocycles DOI
Ravi Kumar, Toshifumi Dohi, Viktor V. Zhdankin

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(9), P. 4786 - 4827

Published: Jan. 1, 2024

This review summarizes structural and synthetic aspects of heterocyclic molecules incorporating an atom a hypervalent main-group element. The higher thermal stability heterocycles, as compared to their acyclic analogs, adds special feature chemistry.

Language: Английский

Citations

8