Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown
Published: Oct. 12, 2024
This report describes a dual catalytic approach for the versatile C-H arylation of arenes under photo-excitation at room temperature. The cooperative catalysis utilizes iron oxide magnetic nanoparticles (which mostly contain Fe
Language: Английский
Chem, Journal Year: 2024, Volume and Issue: 10(6), P. 1940 - 1949
Published: June 1, 2024
The skeletal editing of heteroarenes introduces new disconnections to the chemistry lexicon, enabling interconversion ring systems via selective breaking/re-making carbon framework. We describe one-pot transformation pyridines into benzene derivatives, using a nucleophilic addition ring-opening/ring-closing (ANRORC) process with soft nucleophiles such as malonate. Triflic anhydride activates pyridine ANRORC synthesis an isolable amine intermediate, which aromatizes on simple heating. reaction has been exemplified room temperature protocol, along direct syntheses drug-like, tertiary-alkylated, and isotopically labeled benzoates.
Language: Английский
Citations
12
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
Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(26)
Published: April 18, 2024
C(sp
Language: Английский
Citations
5
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
5
Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)
Published: Aug. 28, 2024
Regioselective C-H functionalization of pyridines remains a persistent challenge due to their inherent electronically deficient properties. In this report, we present strategy for the selective pyridine C3-H thiolation, selenylation, and fluorination under mild conditions via classic N-2,4-dinitrophenyl Zincke imine intermediates. Radical inhibition trapping experiments, as well DFT theoretical calculations, indicated that thiolation selenylation proceeds through radical addition-elimination pathway, whereas two-electron electrophilic substitution pathway. The pre-installed electron-deficient activating N-DNP group plays crucial positive role, with additional benefit recyclability. practicability protocol was demonstrated in gram-scale synthesis late-stage modification pharmaceutically relevant pyridines.
Language: Английский
Citations
4
Chemical Reviews, Journal Year: 2025, Volume and Issue: unknown
Published: March 7, 2025
Constructing chemical bonds under green sustainable conditions has drawn attention from environmental and economic perspectives. The dissociation of (hetero)aryl-halide is a crucial step most arylations affording (hetero)arene derivatives. Herein, we summarize the (hetero)aryl halides activation enabling direct (hetero)arylation trapping reagents construction highly functionalized (hetero)arenes benign conditions. strategies for aryl iodides are classified into (a) hypervalent iodoarene followed by functionalization thermal/photochemical conditions, (b) aryl-I bond in presence bases with/without organic catalysts promoters, (c) photoinduced presence/absence organophotocatalysts, (d) electrochemical direct/indirect electrolysis mediated organocatalysts mediators acting as electron shuttles, (e) electrophotochemical redox-active organocatalysts. These modes result exhibiting diverse reactivity formal cations/radicals/anions aryne precursors. coupling these reactive intermediates with leads to facile selective formation C-C C-heteroatom bonds. ecofriendly, inexpensive, functional group-tolerant offer alternatives transition metal-based catalysis.
Language: Английский
Citations
0
Chem Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 101326 - 101326
Published: March 1, 2025
Language: Английский
Citations
0
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
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
Published: Feb. 6, 2024
The transformation of pyridines into benzene derivatives is described, using a one-pot ANRORC process with soft nucleophiles such as malonate. Triflic anhydride activates the pyridine to synthesis carbocyclic β-aminoester intermediate, which aromatizes on heating. reaction has been exemplified room temperature protocol, along direct syntheses biologi-cally active, tertiary-alkylated and isotopically-labelled benzoates.
Language: Английский
Citations
2