Recent advances in spirocyclization of maleimides via transition-metal catalyzed C–H activation

Organic & Biomolecular Chemistry, Год журнала: 2024, Номер 22(15), С. 2916 - 2947

Опубликована: Янв. 1, 2024

In recent years, the maleimide scaffold has received a great deal of attention in C–H activation.

Язык: Английский

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The literature of heterocyclic chemistry, part XXII, 2022

Advances in heterocyclic chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Язык: Английский

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Copper(I)-Catalyzed Acylation/Cyclization of 2-Aryl-N-acryloyl Indole toward Indolo[2,1-α]isoquinoline Derivatives

Chinese Journal of Organic Chemistry, Год журнала: 2025, Номер 45(1), С. 307 - 307

Опубликована: Янв. 1, 2025

Язык: Английский

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C–H Aminoalkylation of 5-Membered Heterocycles: Influence of Descriptors, Data Set Size, and Data Quality on the Predictiveness of Machine Learning Models and Expansion of the Substrate Space Beyond 1,3-Azoles

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Фев. 11, 2025

We report a general C-H aminoalkylation of 5-membered heterocycles through combined machine learning/experimental workflow. Our work describes previously unknown functionalization reactivity and creates predictive learning (ML) model iterative refinement over 6 rounds active learning. The initial established with 1,3-azoles predicts the reactivities N-aryl indazoles, 1,2,4-triazolopyrazines, 1,2,3-thiadiazoles, 1,3,4-oxadiazoles, while other substrate classes (e.g., pyrazoles 1,2,4-triazoles) are not predicted well. final includes additional heterocyclic scaffolds in training data, which results high accuracy across all tested cores. prediction performance is shown both within set via cross-validation (CV R2 = 0.81) when predicting unseen substrates diverse molecular weight structure (Test 0.95). concept feature engineering discussed, we benchmark mechanistically related DFT-based features that more time-intensive laborious comparison descriptors fingerprints. Importantly, this establishes novel for methods underdeveloped. Since such key motifs drug discovery development, expect to be significant use synthetic synthesis-oriented ML communities.

Язык: Английский

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Imino-λ³-iodane-Triggered Oxidative Ring-Opening of 2H-Indazoles to ortho-N-Acylsulfonamidated Azobenzenes

Organic Letters, Год журнала: 2023, Номер 25(22), С. 4183 - 4187

Опубликована: Май 31, 2023

An iminoiodane-enabled oxidative ring-opening of 2H-indazoles via C-N bond cleavage has been developed under metal-free reaction conditions. This methodology afforded a new array unsymmetrical ortho-N-acylsulfonamidated azobenzenes with wide functional group tolerance in good yields. The potentially proceeds through the formation zwitterionic adduct, which is formed by between and iminoiodane.

Язык: Английский

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Cell Voltage-Dependent Structural Dichotomy: Electrochemical C–H Acyloxylation and N-Acylation of 2H-Indazoles

Organic Letters, Год журнала: 2023, Номер 25(29), С. 5421 - 5425

Опубликована: Июль 14, 2023

A simple and efficient electrochemical method that utilizes modulation of the cell voltage to cause structural alterations in 2H-indazole is introduced. This enables C-3 acyloxylation promotes transfer acyl group from N-1, allowing N-acylation 2H-indazoles. Additionally, application μ-electro flow reactor was demonstrated, showcasing its effectiveness achieving gram-scale production 3x within a short residence time.

Язык: Английский

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Cu-Catalyzed Regioselective C–H Amination of 2H-Indazoles for the Synthesis of Indazole-Containing Indazol-3(2H)-ones

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(9), С. 5731 - 5744

Опубликована: Март 30, 2023

A copper-catalyzed C3 amination of 2H-indazoles with and indazol-3(2H)-ones under mild conditions was developed. series indazole-containing indazol-3(2H)-one derivatives were produced in moderate to excellent yields. The mechanistic studies suggest that the reactions probably proceed through a radical pathway.

Язык: Английский

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Aryliodonium Salt-Induced Regioselective Access to meta-Substituted Anilines by Arylation of Azoles

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(22), С. 16282 - 16291

Опубликована: Фев. 22, 2024

A highly efficient aryliodonium salt-induced regioselective access to meta-substituted anilines by arylation of azoles has been developed under catalyst-free conditions. This transformation provides a facile and scalable approach wide range biologically active N-arylazoles with moderate high yields. According the control experiments, two plausible pathways, including Michael pathway free radical coupling pathway, for reaction were proposed.

Язык: Английский

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Design and Synthesis of Indazole–Indole Hybrid via tert-Butyl Nitrite Mediated Cascade Diazotization/Isomerization/Cyclization

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(10), С. 7295 - 7302

Опубликована: Апрель 25, 2024

In this report, a tert-butyl nitrite (TBN)-mediated straightforward metal-free approach has been presented for the synthesis of diverse range C-3-substituted indazole–indole hybrids using readily accessible 2-(indolin-3-ylidenemethyl)aniline derivatives. This strategy is proposed to occur via diazonium salt intermediate that capable cascade isomerization and intramolecular C–N bond formation through 5-endo-dig cyclization achieve wide variety in good yields.

Язык: Английский

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The C-3 Functionalization of 1H-Indazole through Suzuki–Miyaura Cross-Coupling Catalyzed by a Ferrocene-Based Divalent Palladium Complex Immobilized over Ionic Liquid, as Well as Theoretical Insights into the Reaction Mechanism

Applied Sciences, Год журнала: 2023, Номер 13(7), С. 4095 - 4095

Опубликована: Март 23, 2023

The C-3 functionalization of 1H-indazole could produce a lot highly valuable pharmaceutical precursors, which be used for the treatment cancer and many other inflammatory diseases. This work was focused on through Suzuki–Miyaura cross-coupling 3-iodo-1H-indazole with organoboronic acids, catalyzed by various palladium catalysts immobilized over imidazolium ionic liquids, as well catalyst recycling. A series reaction parameters, including substrate, catalyst, liquid, were fully investigated. It is significant to note that yields present mainly determined solvent used, more than chemical structure substrate. Furthermore, ferrocene-based divalent complexes showed better catalytic outputs compared simple salts. Moreover, using two BMImX (BMIm+ = 1-n-butyl-3-methylimidazolium, X− BF4−, PF6−) not only improved cross-coupled products, but also avoided formation Pd(0) black, non-ionic liquid facilitated reactions, simultaneously making recycling effective. On average, BMImBF4 performed BMImPF6. Additionally, scientific calculations revealed 1,1′-bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex (PdCl2(dppf)) lower energy barrier in intermediates [1,1′-bis(di-tert-butylphosphino)ferrocene]dichloropalladium(II) (PdCl2(dtbpf)), leading higher outputs. may contribute development 1H-indazole-derived new pharmaceuticals.

Язык: Английский

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