Photoinduced Cu(II)‐Mediated Decarboxylative Thianthrenation of Aryl and Heteroaryl Carboxylic Acids DOI Creative Commons
Zhen He, Paweł Dydio

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

Published: July 16, 2024

Given that (hetero)aryl carboxylic acids are inexpensive materials available in a great variety from commercial and natural resources or synthesis, the strategies enabling their use as starting for preparing fine chemicals highly sought after. Here we report photoinduced Cu(II)-mediated protocol converting into thianthrenium salts, high value-added building blocks can undergo various subsequent transformations, creating an attractive two-step pathway divergent functionalization of these ubiquitous materials. The excellent compatibility method is shown by broad range sterically electronically varied including derivatives pharmaceuticals, such ataluren, celecoxib, flavoxate, probenecid, repaglinide, tamibarotene. syntheses 13 C-labeled probenecid bioisosteres ataluren well unconventional modifications celecoxib illustrate synthetic potential strategy. Mechanistic studies line with reaction occurring through ligand-to-metal charge transfer (LMCT) Cu(II)-arylcarboxylates, radical decarboxylative carbometallation to form arylcopper(II) intermediates turn react thianthrene product. Noteworthy, susceptibility aryl salts photodegradation overcome Cu(I)-driven salvage loop, which continuously intercepts transiently formed radicals regenerates products.

Language: Английский

Photoinduced Copper-Catalyzed Late-Stage Azidoarylation of Alkenes via Arylthianthrenium Salts DOI Creative Commons
Yuan Cai, Sagnik Chatterjee, Tobias Ritter

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(25), P. 13542 - 13548

Published: June 12, 2023

The arylethylamine pharmacophore is conserved across a range of biologically active natural products and pharmaceuticals, particularly in molecules that act on the central nervous system. Herein, we present photoinduced copper-catalyzed azidoarylation alkenes at late stage with arylthianthrenium salts, allowing access to highly functionalized acyclic (hetero)arylethylamine scaffolds are otherwise difficult access. A mechanistic study consistent rac-BINAP-CuI-azide (2) as photoactive catalytic species. We show utility new method by expedient synthesis racemic melphalan four steps through C-H functionalization.

Language: Английский

Citations

82
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
Thianthrenium-Enabled Phosphorylation of Aryl C–H Bonds via Electron Donor–Acceptor Complex Photoactivation DOI
Hao Xu, Xufeng Li,

Yuzheng Dong

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(20), P. 3784 - 3789

Published: May 16, 2023

An efficient strategy for the preparation of aryl phosphonates via blue-light-promoted single electron transfer process an EDA complex between phosphites and thianthrenium salts has been demonstrated. The corresponding substituted were obtained in good to excellent yields, byproduct thianthrene can be recovered reused quantity. This developed method realizes construction through indirect C-H functionalization arenes, which potential application value drug discovery development.

Language: Английский

Citations

43
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

41
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

18
Modular assembly of arenes, ethylene and heteroarenes for the synthesis of 1,2-arylheteroaryl ethanes DOI
Tao Liu, T. Li,

Zhi Yuan Tea

et al.

Nature Chemistry, Journal Year: 2024, Volume and Issue: 16(10), P. 1705 - 1714

Published: June 27, 2024

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

14
Modular and Practical 1,2‐Aryl(Alkenyl) Heteroatom Functionalization of Alkenes through Iron/Photoredox Dual Catalysis** DOI Creative Commons
Weigang Zhang, Tao Liu, Hwee Ting Ang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(44)

Published: Sept. 13, 2023

Abstract Efficient methods for synthesizing 1,2‐aryl(alkenyl) heteroatomic cores, encompassing heteroatoms such as nitrogen, oxygen, sulfur, and halogens, are of significant importance in medicinal chemistry pharmaceutical research. In this study, we present a mild, versatile practical photoredox/iron dual catalytic system that enables access to highly privileged pharmacophores with exceptional efficiency site selectivity. Our approach exhibits an extensive scope, allowing the direct utilization wide range commodity or commercially available (hetero)arenes well activated unactivated alkenes diverse functional groups, drug scaffolds, natural product motifs substrates. By merging iron catalysis photoredox cycle, vast array alkene functionalization products incorporate neighboring azido, amino, halo, thiocyano nitrooxy group were secured. The scalability ability rapid synthesize numerous bioactive small molecules from readily starting materials highlight utility protocol.

Language: Английский

Citations

19
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