Visible-light-induced Ir-catalyzed site-selective C−H trifluoromethylation of 3-substituted 1,2-benzoxazoles DOI

Ming-Ming Xiao,

Mingqing Hua,

Fangyou Mou

et al.

Chemistry of Heterocyclic Compounds, Journal Year: 2024, Volume and Issue: 60(5-6), P. 299 - 303

Published: June 1, 2024

Language: Английский

Mechanosynthesis of polysubstituted pyridines via FeBr3-catalyzed cascade reaction of arylidene isoxazolones with β‑carbonyl esters DOI
Lei Wang, Mingjun Li, Qinghai Li

et al.

Tetrahedron Letters, Journal Year: 2025, Volume and Issue: unknown, P. 155569 - 155569

Published: March 1, 2025

Language: Английский

Citations

0
Visible-light-induced meta-selective sulfonylation of pyridine via an EDA complex DOI

Yong-Qing Ye,

Zhipeng Ye,

Meng Guo

et al.

Chemical Communications, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Pyridine is a versatile structural unit found in broad spectrum of pharmaceuticals, agrochemicals, and materials. Achieving selective meta-functionalization under mild conditions remains challenging due to its inherent electronic properties. In this work, we accomplished photoinduced method for meta-selective sulfonylation pyridines, facilitated by an electron donor-acceptor (EDA) complex between iodide ions sulfonyl chlorides. The reaction proceeds via oxazino-pyridine intermediate, with chloride acting as the radical precursor. This protocol stands out mild, photocatalyst-free conditions, high C5-selectivity, good scalability, offering promising approach synthesis meta-sulfonylated pyridines.

Language: Английский

Citations

0
Site-selective electrochemical C–H silylations of pyridines enabled by temporary reductive dearomatization DOI
Zhihao Yang, Xuan Liu, Tianyuan Zhang

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(19), P. 5545 - 5552

Published: Jan. 1, 2024

Site-selective silylations of electron-deficient pyridines is presented, the C4-to-C5 selectivity can be controlled by adjusting bulkiness chlorosilanes.

Language: Английский

Citations

3
Advances in Pyridine C – H Functionalizations: Beyond C2 Selectivity DOI
Sachin Balaso Mohite, Yafia Kousin Mirza, Partha Sarathi Bera

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 31(2)

Published: Nov. 28, 2024

The pyridine core is a crucial component in numerous FDA-approved drugs and Environmental Protection Agency (EPA) regulated agrochemicals. It also plays significant role ligands for transition metals, alkaloids, catalysts, various organic materials with diverse properties, making it one of the most important structural frameworks. However, despite its significance, direct selective functionalization still relatively underdeveloped due to electron-deficient nature strong coordinating ability nitrogen. Among variety synthetic transformation, C-H bond straightforward atom economical approach it's advantageous late-stage containing drugs. In recent years, innovative strategies regioselective pyridines azines have emerged, offering benefits such as high regioselectivity, mild conditions, enabling transformations that were challenging traditional methods. This review emphasizes latest advancements meta para-C-H through approaches, including phosphonium salts, photocatalytic methods, temporary de-aromatization, Minisci-type reactions, metal-catalyzed activation techniques. We discuss advantages limitations these current methods aim inspire further progress this field.

Language: Английский

Citations

3
Directing group-assisted selective C–H activation of six-membered N-heterocycles and benzo-fused N-heterocycles DOI
Smruti Ranjan Mohanty, Namrata Prusty, Tanmayee Nanda

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 11(2), P. 540 - 575

Published: Dec. 7, 2023

Directing group-assisted selective C–H bond activation of six-membered N-heterocycles and benzo-fused has been reported.

Language: Английский

Citations

8
The Construction of Highly Substituted Piperidines via Dearomative Functionalization Reaction DOI Creative Commons
Miao Hu, Hao Ding, William DeSnoo

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(49)

Published: Oct. 20, 2023

Nitrogen heterocycles play a vital role in pharmaceuticals and natural products, with the six-membered aromatic aliphatic architectures being commonly used. While synthetic methods for N-heterocycles are well-established, synthesis of their functionalized analogues, particularly piperidine derivatives, poses significant challenge. In that regard, we propose stepwise dearomative functionalization reaction construction highly decorated derivatives diverse functional handles. We also discuss challenges related to site-selectivity, regio- diastereoselectivity, provide insights into mechanism through mechanistic studies density theory computations.

Language: Английский

Citations

7
Catalyst-free visible light-promoted defunctionalization of alkyl isocyanides with a hydrosilane through C–N bond cleavage DOI
Yu‐Qing Ma, Shi‐Kai Tian

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(13), P. 2562 - 2565

Published: Jan. 1, 2024

Various alkyl isocyanides participated in the defunctionalization with tris(trimethylsilyl)silane under blue light irradiation at room temperature high chemoselectivity.

Language: Английский

Citations

2
Purple Light-Promoted Coupling of Bromopyridines with Grignard Reagents via SET DOI
Xingyu Lei, Yihan Wang, Shanshan Ma

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(10), P. 7148 - 7155

Published: May 8, 2024

Alkyl- and arylpyridines 2,2′-bipyridines are conventionally prepared by Minisci reactions of pyridines transition metal-catalyzed coupling halopyridines. Herein, purple light-promoted radical 2- or 4-bromopyridines with Grignard reagents in Et2O a mixture tetrahydrofuran regular glassware without the need for metal catalyst were disclosed first time. Methyl, primary secondary alkyl, cycloalkyl, aryl, heteroaryl, pyridyl, alkynyl compatible protocol. As result, alkyl- easily prepared. Single electron transfer from reagent to bromopyridine was stimulated light. An extruded dimerization worked as catalyst. Light on/off experiments indicated that constant irradiation required product formation. Studies clock substrates verified involvement pyridyl noninvolvement an alkyl aryl reagent. The available proof supports photoinduced SRN mechanism new reactions.

Language: Английский

Citations

2
para-Selective radical alkylation of pyridines with diacyl peroxides and peresters DOI
Zhe Wang, Pengwei Xu, Armido Studer

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(14), P. 3849 - 3854

Published: Jan. 1, 2024

A regioselective para -alkylation of pyridines using alkyl carboxylic acid-derived diacyl peroxides or peresters is reported. This reaction proceeds under mild conditions, and late-stage functionalization complex can be realized.

Language: Английский

Citations

2
Silyl Radical as an Isocyanide Transfer Agent for Giese-Type Reactions Involving Aliphatic Amines DOI

Yuqing Ma,

Muliang Zhang, Shi‐Kai Tian

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(24), P. 5172 - 5176

Published: June 12, 2024

Herein we report silyl radicals serve as isocyanide transfer agents for Giese-type reaction from aliphatic amines and electron-deficient olefins. α-Primary, α-secondary, sterically encumbered α-tertiary primary could be easily converted into isocyanides coupling with olefins by employing latent under visible light irradiation. Notably, the abstraction of silane-mediated not only enables voltage-independent activation strong C-N bonds but also represents a mechanistic alternative in which single electron reduction protonation processes are replaced direct hydrogen atom transfer. This transformation occurs photoinduced catalyst-free conditions exhibits excellent functional group compatibility mild conditions.

Language: Английский

Citations

2