Electrochemical meta-C−H Sulfonylation of Pyridines with Nucleophilic Sulfinates DOI Creative Commons
Zhongyi Zeng,

Qin Shi,

Mingkai Yang

и другие.

Research Square (Research Square), Год журнала: 2024, Номер unknown

Опубликована: Апрель 23, 2024

Abstract 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 extremely 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 unprecedented 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.

Язык: Английский

Synthesis of 15N-Pyridines and Higher Mass Isotopologs via Zincke Imine Intermediates DOI
Hillary M. H. Nguyen, D. Thomas, Marie A. Hart

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(5), С. 2944 - 2949

Опубликована: Янв. 16, 2024

Methods to incorporate stable radioisotopes are integral pharmaceutical and agrochemical development. However, despite the prevalence of pyridines in candidate compounds, methods 15N atoms within their structures limited. Here, we present a general approach pyridine 15N-labeling that proceeds via ring-opening NTf-Zincke imines then ring-closure with commercially available 15NH4Cl salts. This process functions on range substituted pyridines, from simple building block-type compounds late-stage labeling complex pharmaceuticals, 15N-incorporation is >95% most cases. The reactivity Zincke imine intermediates also enables deuteration C3- C5-positions, resulting higher mass isotopologs required for LCMS analysis biological fluids during drug

Язык: Английский

Процитировано

24
A deconstruction-reconstruction strategy for pyrimidine diversification DOI

Benjamin J. H. Uhlenbruck,

Celena M. Josephitis,

Louis de Lescure

и другие.

Nature, Год журнала: 2024, Номер 631(8019), С. 87 - 93

Опубликована: Май 2, 2024

Язык: Английский

Процитировано

20
Electrochemical meta-C–H sulfonylation of pyridines with nucleophilic sulfinates DOI Creative Commons

Qin Shi,

Mingkai Yang,

Mingyao Xu

и другие.

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Авг. 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.

Язык: Английский

Процитировано

9
C3 Selective chalcogenation and fluorination of pyridine using classic Zincke imine intermediates DOI Creative Commons
Shun Li, Juan Tang,

Yonglin Shi

и другие.

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Авг. 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.

Язык: Английский

Процитировано

6
Ultrafast Energy Transfer Induced Lasing From a Coplanar Donor‐Acceptor‐Donor Molecule in a Microspherical Cavity DOI Creative Commons
Vishal Kumar, Soh Kushida,

Takeru Inoue

и другие.

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Апрель 7, 2025

Abstract Intramolecular excitation energy transfer (IET) dynamics and molecular rigidity of a donor‐acceptor system control the lasing efficiency organic gain media. Herein, novel molecule COPV2‐3‐2 , featuring carbon‐bridged oligo( para ‐phenylenevinylenes) (COPV) is reported. In this structure, COPV2 COPV3 serve as photo‐absorptive donor emissive acceptor monomer units, respectively, two identical donors are connected to coplanarly arranged through rigid orthogonal bridges. The rational design donor‐bridge‐acceptor‐bridge‐donor (D‐B‐A‐B‐D) ensures precise over IET enables four‐level for efficient at emission band. Time‐resolved studies using femtosecond‐transient absorption spectroscopy unveil that exhibits near unity intramolecular with an ultrafast rate constant 2.27 ps −1 . Additionally, singlet‐singlet annihilation (SSA) also observed pump fluence 115 µJ cm −2 which can hinder population inversion. To suppress threshold below SSA, doped into polystyrene matrix fabricate high Q ‐factor microspherical cavity. This microcavity whispering gallery mode (WGM) averaged low (≈104 ), ‐factors (≈1180), excellent photostability half‐life (≈10 5 pulses), demonstrating potential optical material advanced photonic applications.

Язык: Английский

Процитировано

0
3-Selective Pyridine Fluorination via Zincke Imine Intermediates DOI
Marie A. Hart,

Benjamin J. H. Uhlenbruck,

Jeffrey N. Levy

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Май 20, 2025

Fluorine substitution is a widely used approach to improve the properties of drugs bearing aromatic rings and has spawned numerous new methods for C-F bond formation. Reactions employing C-H precursors are particularly valuable, but pyridine-applicable variants rare, especially at C3-position. We developed an using ring-opened Zincke imines that undergo regioselective formation with electrophilic fluorination reagents, resulting in C3-fluoropyridines after ring closure. This process can accommodate wide range pyridine patterns, tolerates various appended functional groups, viable late-stage pyridine-containing drugs.

Язык: Английский

Процитировано

0
Photochemical C3-amination of pyridines via Zincke imine intermediates DOI Creative Commons
Kitti Franciska Szabó, Piotr Banachowicz, Antoni Powała

и другие.

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Май 31, 2025

Язык: Английский

Процитировано

0
Electrochemical meta-C−H Sulfonylation of Pyridines with Nucleophilic Sulfinates DOI Creative Commons
Zhongyi Zeng,

Qin Shi,

Mingkai Yang

и другие.

Research Square (Research Square), Год журнала: 2024, Номер unknown

Опубликована: Апрель 23, 2024

Abstract 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 extremely 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 unprecedented 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.

Язык: Английский

Процитировано

0