Visible‐Light‐Initiated Uranyl‐Catalyzed Hydrosilylation and Hydrosulfonylation of Alkenes and Alkynes DOI Open Access

Xingxing Gong,

Qianyi Zhao, Congqing Zhu

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 27, 2024

Abstract This study investigates the visible‐light‐initiated uranyl(VI)‐catalyzed activation of Si−H bonds through direct hydrogen atom transfer, which facilitates formation silyl radicals from silanes. The radical can abstract a chlorine sulfonyl chloride, leading to generation radicals. These and could react with alkenes alkynes, achieving first example uranyl‐catalyzed hydrosilylation hydrosulfonylation unsaturated C−C bonds. method features mild reaction conditions broad substrate scope, exhibits exceptional functional‐group tolerance. Consequently, it is suitable for late‐stage functionalization drug derivatives.

Language: Английский

Introduction of the difluoromethyl group at the meta- or para-position of pyridines through regioselectivity switch DOI Creative Commons
Pengwei Xu, Zhe Wang, Shu‐Min Guo

et al.

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

Published: May 15, 2024

Abstract Difluoromethyl pyridines have gained significant attention in medicinal and agricultural chemistry. The direct C−H-difluoromethylation of represents a highly efficient economic way to access these azines. However, the meta-difluoromethylation has remained elusive methods for site-switchable regioselective meta- para-difluoromethylation are unknown. Here, we demonstrate meta-C−H-difluoromethylation through radical process by using oxazino pyridine intermediates, which easily accessed from pyridines. selectivity can be readily switched para situ transformation pyridinium salts upon acid treatment. preparation various para-difluoromethylated this approach is presented. mild conditions used also allow late-stage or containing drugs. Sequential double functionalization presented, further underlines value work.

Language: Английский

Citations

14
meta-Nitration of Pyridines and Quinolines through Oxazino Azines DOI
Kuruva Balanna, Armido Studer

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: 147(9), P. 7485 - 7495

Published: Feb. 24, 2025

meta-Nitration of azines (pyridines and quinolines) serves as a powerful method for the prompt construction derivatization several pharmaceuticals, agrochemicals, materials. However, due to inherent electronic properties pyridines, achieving direct selective meta-C-H nitration under mild conditions has been long-standing challenge in synthetic chemistry. Currently, there is no adequate strategy late-stage pyridine-containing drugs drug precursors. To address this void, we introduce practical protocol highly regioselective meta-nitration pyridines using dearomatization-rearomatization strategy. The introduced provides diversification platform at meta-position via radical pathway. This mild, open-air, one-pot, scalable, catalyst-free process employed pyridine containing drugs, precursors, ligands limiting reagents. Consecutive C3 C5 difunctionalization also achieved with complete regiocontrol relying on sequential addition, which further highlights potential presented work. Additionally, obtained products could be transformed into meta-amino azine other valuable building blocks. Incorporating N-heterocyclic amine structures through amidation ibuprofen significantly improved drug's clinical success, highlighting importance

Language: Английский

Citations

2
Electrochemical meta-C–H sulfonylation of pyridines with nucleophilic sulfinates DOI Creative Commons

Qin Shi,

Mingkai Yang,

Mingyao Xu

et al.

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

Published: Aug. 28, 2024

Considering the indispensable significance and utilities of meta-substituted pyridines in medicinal, chemical as well materials science, a direct meta-selective C-H functionalization is paramount importance, but such reactions remain limited highly challenging. In general, established methods for meta rely on utilization tailored electrophilic reagents to realize intrinsic polarity match. Herein, we report complementary electrochemical methodology; diverse nucleophilic sulfinates allow meta-sulfonylation through redox-neutral dearomatization-rearomatization strategy by tandem dearomative cycloaddition/hydrogen-evolution electrooxidative sulfonation resulting oxazino-pyridines/acid-promoted rearomatization sequence. Besides, several salient features, including exclusive regiocontrol, remarkable substrate/functional group compatibility, scale-up potential, facile late-stage modification, have been demonstrated, which further contributes practicality adaptability this approach.

Language: Английский

Citations

9
C3 Selective Hydroxylation of Pyridines via Photochemical Valence Isomerization of Pyridine N-Oxides DOI

Chen-Yan Cai,

Si-Jie Chen,

Rohan R. Merchant

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(35), P. 24257 - 24264

Published: Aug. 22, 2024

The C–H hydroxylation of the pyridine C3 position is a highly desirable transformation but remains great challenge due to inherent electronic properties this heterocycle core which bring difficulties in chemical reactivity and regioselectivity. Herein we present an efficient method for formal selective pyridines via photochemical valence isomerization N-oxides. This metal-free features operational simplicity compatibility with diverse array functional groups, resulting hydroxylated products are amenable further elaboration synthetically useful building blocks. synthetic utility strategy demonstrated effective late-stage functionalization pyridine-containing medicinally relevant molecules versatile derivatizations 3-pyridinols.

Language: Английский

Citations

8
Unified ionic and radical C-4 alkylation and arylation of pyridines DOI Creative Commons

Qiu Shi,

Xiaofeng Huang, Ruizhi Yang

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(31), P. 12442 - 12450

Published: Jan. 1, 2024

A practical and general C-4 functionalization strategy of unbiased pyridines is developed by identifying a readily synthesized substituted urea as the pyridine activation reagent.

Language: Английский

Citations

6
Meta‐Selective Copper‐Catalyzed C−H Arylation of Pyridines and Isoquinolines through Dearomatized Intermediates DOI Creative Commons
Shu‐Min Guo, Pengwei Xu, Armido Studer

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(26)

Published: April 18, 2024

C(sp

Language: Английский

Citations

5
Metal-free assembly of diverse polysubstituted pyridines via an efficient cascade approach using tertiary enaminones and α,β-unsaturated sulfonylketimines DOI
Xiang Li, Qiwen Pang, Yang Zhang

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(9), P. 2607 - 2612

Published: Jan. 1, 2024

A metal-free, scalable, and cascade protocol for assembling diverse polysubstituted pyridines from tertiary enaminones α,β-unsaturated sulfonylketimines by cleaving C–N/N–S bonds is reported.

Language: Английский

Citations

4
1,3-Difunctionalization of [1.1.1]propellane through iron-hydride catalyzed hydropyridylation DOI Creative Commons

Changha Kim,

Yuhyun Kim, Sungwoo Hong

et al.

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

Published: July 16, 2024

Current methodologies for the functionalization of [1.1.1]propellane primarily focus on achieving 1, 3-difunctionalized bicyclo[1.1.1]pentane or ring-opened cyclobutane moiety. Herein, we report an innovative approach 3-difunctionalization [1.1.1]propellane, enabling access to a diverse range highly functionalized cyclobutanes via nucleophilic attack followed by ring opening and iron-hydride hydrogen atom transfer. To enable this method, developed efficient iron-catalyzed hydropyridylation various alkenes C - H alkylation pyridines at C4 position, eliminating need stoichiometric quantities oxidants reductants. Mechanistic investigations reveal that resulting N-centered radical serves as effective oxidizing agent, facilitating single-electron transfer oxidation reduced iron catalyst. This process efficiently sustains catalytic cycle, offering significant advantages substrates with oxidatively sensitive functionalities are generally incompatible alternative approaches. The strategy presented herein is not only mechanistically compelling but also demonstrates broad versatility, highlighting its potential late-stage functionalization.

Language: Английский

Citations

4
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

4
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

4