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

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(35), С. 24257 - 24264

Опубликована: Авг. 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.

Язык: Английский

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Formal meta-C–H-Fluorination of Pyridines and Isoquinolines through Dearomatized Oxazinopyridine Intermediates

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(45), С. 30758 - 30763

Опубликована: Ноя. 1, 2024

Organofluorine compounds, including fluorinated pyridines and isoquinolines, play a crucial role in pharmaceuticals, agrochemicals, materials science. However, step-economic selective C-H-functionalization to access these azaarenes is still underexplored, with

Язык: Английский

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Photoinduced Metal‐/Additive‐Free Difluoromethylation of N‐Heteroaromatics^†

Chinese Journal of Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 16, 2025

Comprehensive Summary Herein, we report a photo‐induced, metal‐/additive‐free protocol for the difluoromethylation of N ‐heteroaromatics with [bis(difluoroacetoxy)iodo]benzene as reagent. The affords difluoromethylated in moderate to good yield (up 91%). transformation is compatible wide range substrates and has tolerance towards various functional groups. Moreover, synthetic value this method further demonstrated by applications gram‐scale synthesis late‐stage functionalization biologically important molecules.

Язык: Английский

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Unlocking redox-active reactivity of dearomatized pyridines with photochemistry toward meta-C–H functionalization of pyridines

Chem Catalysis, Год журнала: 2025, Номер unknown, С. 101326 - 101326

Опубликована: Март 1, 2025

Язык: Английский

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Electrochemical Access to Difluoromethyl Groups: An Overview of Scope, Mechanisms, and Challenges

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 6826 - 6851

Опубликована: Апрель 14, 2025

Язык: Английский

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Advances in Pyridine C – H Functionalizations: Beyond C2 Selectivity

Chemistry - A European Journal, Год журнала: 2024, Номер 31(2)

Опубликована: Ноя. 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.

Язык: Английский

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Insight into C4 Selectivity in the Light‐Driven C–H Fluoroalkylation of Pyridines and Quinolines

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(46)

Опубликована: Авг. 9, 2024

Abstract Given the prevalence of pyridine motifs in FDA‐approved drugs, selective fluoroalkylation pyridines and quinolines is essential for preparing diverse bioisosteres. However, challenges are often faced with conventional Minisci reactions achieving precise regioselectivity owing to competing reaction sites limited availability fluoroalkyl radical sources. Herein, we present a light‐driven, C4‐selective azines utilizing N‐aminopyridinium salts readily available sulfinates. Our approach employs electron donor‐acceptor complexes, highly under mild conditions without an external photocatalyst. This practical method not only enables installation CF 2 H groups but also allows incorporation ‐alkyl functional entities, surpassing limitations previous methods. The versatility pathway further demonstrated through straightforward three‐component involving alkenes [1.1.1]propellane. Detailed experimental computational studies have elucidated origins regioselectivity, providing profound insights into mechanistic aspects.

Язык: Английский

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Quinazoline derivatives inhibit cell growth of prostate cancer as a WRN helicase dependent manner by regulating DNA damage repair and microsatellite instability

Bioorganic Chemistry, Год журнала: 2024, Номер 153, С. 107963 - 107963

Опубликована: Ноя. 14, 2024

Язык: Английский

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Unraveling C4 selectivity in the light-driven C–H fluoroalkylation of pyridines and quinolines

Опубликована: Май 28, 2024

Given the prevalence of pyridine motifs in FDA-approved drugs, selective fluoroalkylation pyridines and quinolines is essential for preparing diverse bioisosteres. However, conventional Minisci reactions often face challenges achieving precise regioselectivity due to competing reaction sites limited availability fluoroalkyl radical sources. Herein, we present a light-driven, C4-selective azines utilizing N-aminopyridinium salts readily available sulfinates. Our approach employs electron donor-acceptor complexes, highly under mild conditions without an external photocatalyst. This practical method not only enables installation CF2H groups but also allows incorporation CF2-alkyl with functional entities, surpassing limitations previous methods. The versatility pathway further demonstrated through straightforward three-component involving alkenes [1.1.1]propellane. Detailed experimental computational studies have elucidated origins regioselectivity, providing profound insights into mechanistic aspects.

Язык: Английский

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Insight into C4 Selectivity in the Light‐Driven C–H Fluoroalkylation of Pyridines and Quinolines

Angewandte Chemie, Год журнала: 2024, Номер 136(46)

Опубликована: Авг. 9, 2024

Abstract Given the prevalence of pyridine motifs in FDA‐approved drugs, selective fluoroalkylation pyridines and quinolines is essential for preparing diverse bioisosteres. However, challenges are often faced with conventional Minisci reactions achieving precise regioselectivity owing to competing reaction sites limited availability fluoroalkyl radical sources. Herein, we present a light‐driven, C4‐selective azines utilizing N‐aminopyridinium salts readily available sulfinates. Our approach employs electron donor‐acceptor complexes, highly under mild conditions without an external photocatalyst. This practical method not only enables installation CF 2 H groups but also allows incorporation ‐alkyl functional entities, surpassing limitations previous methods. The versatility pathway further demonstrated through straightforward three‐component involving alkenes [1.1.1]propellane. Detailed experimental computational studies have elucidated origins regioselectivity, providing profound insights into mechanistic aspects.

Язык: Английский

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