Radical Replacement Process for Ligated Boryl Radical-Mediated Activation of Unactivated Alkyl Chlorides for C(sp³)–C(sp³) Bond Formation

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Сен. 12, 2024

The ligated boryl radical (LBR) has emerged as a potent tool for activating alkyl halides in transformations through halogen-atom transfer (XAT). However, unactivated chlorides still present an open challenge this strategy. We herein describe new activation mode of the LBR to construct C(sp

Язык: Английский

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Recent Advances in Combining Photo- and N-Heterocycle Nitrenium Catalysis

Synthesis, Год журнала: 2024, Номер unknown

Опубликована: Сен. 19, 2024

Abstract N-Heterocyclic nitreniums (NHNs) are isoelectronic and isostructural analogues of N-heterocyclic carbenes (NHCs). Unlike NHCs, NHNs much less developed. While a comprehensive understanding NHN reactivity remains elusive, recent advancements have demonstrated their utility as Lewis acid catalysts, photoreductants, photooxidants, leading to several reaction patterns. In this short review, we focus on the applications in photoredox reactions. We also discuss mechanisms behind these transformations outline future research directions. 1 Introduction 2 Application Nitreniums Photoreductants 3 Facilitate Photohomolysis 4 Photooxidants 5 Conclusion

Язык: Английский

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N-Heterocyclic nitrenium-catalyzed triple domino reaction of organic iodides for the synthesis of phthalides and δ-lactones

Green Synthesis and Catalysis, Год журнала: 2025, Номер unknown

Опубликована: Апрель 1, 2025

Язык: Английский

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Photoinduced N‑Heterocyclic Nitrenium-Catalyzed Single Electron Reduction of α-Chloro Esters for Phenanthridine Synthesis

Organic & Biomolecular Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

An efficient photoactive charge transfer complex protocol for the synthesis of phenanthridine derivatives by reaction 2-isocyanobiaryls with α-chloro esters is established.

Язык: Английский

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Pyrazolo[1,5-a]pyrimidine-Based Type-I Photosensitizer as an Efficient Pyroptosis Inducer for Tumor Ablation

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

Опубликована: Май 4, 2025

Pyroptosis is a proinflammatory and lytic programmed cell death form, which can promote cytotoxic T lymphocyte (CTL) maturation tumor infiltration through the release of damage-associated molecular patterns (DAMPs). Therefore, induction pyroptosis by small molecules promising strategy to activate antitumor immunity. In this work, we report design new class pyrazolo[1,5-a]pyrimidine-based type-I photosensitizers (PSs) as efficient inducers for cancer photodynamic therapy (PDT). Among compounds, ZS-3 exhibited most excellent reactive oxygen species (ROS) generation ability phototoxicity in vitro. It was found that induced caspase-3/gasdermin E (GSDME) pathway under light irradiation, characterized bubble formation pattern release. Furthermore, lipid nanoparticles significantly inhibited growth evoked immune responses vivo.

Язык: Английский

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Exploring the Electronic Properties of Cyclic Five-Membered 1,2,3-Triazolium Ions: A Quantum Chemical Study

The Journal of Physical Chemistry A, Год журнала: 2025, Номер unknown

Опубликована: Май 17, 2025

Cyclic nitrenium ions (CNIs) are generally stable and have found applications in chemistry, including biochemistry. five-membered 1,2,3-triazolium (CFTIs) a special class of CNIs; such moieties few medicinally important species. Though they isoelectronic to N-heterocyclic carbenes (NHCs), exhibit electrophilic properties (unlike nucleophilic NHCs). A quantum chemical studies were reported, but extensive study on CFTIs is required understand their electronic features design species with tailored properties. In this work, thorough analysis has been carried out the standard CFTI (1,3-dimethyl-1,2,3-triazolium ion). Hydride ion affinity fluoride parameters estimated evaluate Lewis acidic character CFTIs. Also, electrophilicity these terms global index (ω) values. The complexation energies PMe3 (ΔHPMe3) 1,3-dimethylimidazol-2-ylidene (ΔHNHC) also estimated. modulation as function substitution ring fusion evaluated. correlation between ΔHPMe3 ΔHNHC very high (R = 0.99); helps identifying that may character.

Язык: Английский

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Orchestrated Octuple C–H Activation: A Bottom‐Up Topology Engineering Approach toward Stimuli‐Responsive Double‐Heptagon‐Embedded Wavy Polycyclic Heteroaromatics

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(31)

Опубликована: Май 17, 2024

Curiosity-driven innovations on the design and synthesis of nonplanar polycyclic aromatic/heteroaromatic compounds with new molecular topologies unfold exciting opportunities for harnessing their intriguing supramolecular properties thereby development novel functional organic materials. This work presents such an innovative synthetic concept a bottom-up topology engineering through unique orchestrated octuple C-H activation reaction, toward rapid class double heptagon-incorporated nitrogen-doped laterally-fused rarely reported wavy structural configuration. The profound impact structures these is manifested by weak tunable solid-state intermolecular interactions controlling electronic materials, leading to reversibly switchable fluorochromism in solid state thin films mechanical force solvent vapors as external stimuli, indicating potential applicability rewritable fluorescent optical recording media, security papers, mechanosensors, volatile compound (VOC) sensors etc.

Язык: Английский

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Stable, aromatic, and electrophilic azepinium ions: Design using quantum chemical methods

Journal of Computational Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Окт. 30, 2024

Abstract Cyclic nitrenium ions containing five‐membered and six‐membered rings are available, however, the seven‐membered cyclic (azepinium ions) rare. The chemistry of these species is related to their stability originating from aromaticity due 6π electrons. Very few theoretical experimental studies have been conducted on azepinium ions. Related clozapine olanzapine cations (diazepinium were observed during drug metabolism studies. In this work, quantum chemical analysis has carried out estimate stability, aromaticity, electrophilicity several derivatives A designed carry Δ E S‐T values in range 50 kcal/mol favoring singlet state; π donating groups at 2nd position increase singlet‐triplet energy differences. Most substituents reduce NICS(1) compared parent system. Ring fusion with heterocyclic generally increases ion ring systems. parameters estimated terms HIA, FIA, ω indicate that it possible fine‐tune properties appropriate modulation.

Язык: Английский

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Synthesis of π-Extended Imidazo[1,2-a]quinolines via Carboxylic Acid-Assisted Ru(II)-Catalyzed Dual C–H Activation and Alkyne Annulation

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 27, 2024

Ru(II)-catalyzed, carboxylic acid-assisted oxidative annulation of

Язык: Английский

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Orchestrated Octuple C–H Activation: A Bottom‐Up Topology Engineering Approach toward Stimuli‐Responsive Double‐Heptagon‐Embedded Wavy Polycyclic Heteroaromatics

Angewandte Chemie, Год журнала: 2024, Номер 136(31)

Опубликована: Май 17, 2024

Abstract Curiosity‐driven innovations on the design and synthesis of nonplanar polycyclic aromatic/heteroaromatic compounds with new molecular topologies unfold exciting opportunities for harnessing their intriguing supramolecular properties thereby development novel functional organic materials. This work presents such an innovative synthetic concept a bottom‐up topology engineering through unique orchestrated octuple C−H activation reaction, toward rapid class double heptagon‐incorporated nitrogen‐doped laterally‐fused rarely reported wavy structural configuration. The profound impact structures these is manifested by weak tunable solid‐state intermolecular interactions controlling electronic materials, leading to reversibly switchable fluorochromism in solid state thin films mechanical force solvent vapors as external stimuli, indicating potential applicability rewritable fluorescent optical recording media, security papers, mechanosensors, volatile compound (VOC) sensors etc.

Язык: Английский

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