Triazenolysis of Alkenes: Aza-version of Ozonolysis DOI Creative Commons
Mark Gandelman, Alexander N. Koronatov, Pavel А. Sakharov

и другие.

Research Square (Research Square), Год журнала: 2023, Номер unknown

Опубликована: Окт. 30, 2023

Abstract Numerous applications of alkenes exist due to their abundance and versatility in chemical transformations. In this study, we present a unique novel transformation alkenes, the aza-version canonical ozonolysis reaction, which termed as triazenolysis. This process offers non-trivial previously unfeasible synthetic disconnection, allowing cleavage C=C double bond into two new C-N bonds reductive manner. We carefully examined applicability finding that diverse cyclic are suitable for developed process. Furthermore, an example acyclic alkene, illustrating potential expanding triazenolysis other counterparts. Through DFT calculations, explored mechanism key step demonstrated significance Lewis acid catalysis achieving desired transformation.

Язык: Английский

Triazenolysis of alkenes as an aza version of ozonolysis DOI
Alexander N. Koronatov, Pavel А. Sakharov, Deepak Ranolia

и другие.

Nature Chemistry, Год журнала: 2024, Номер 17(1), С. 101 - 110

Опубликована: Окт. 11, 2024

Язык: Английский

Процитировано

3
Recent Advances in Combining Photo- and N-Heterocycle Nitrenium Catalysis DOI

Yongliang Tu,

Xiangyu Chen, Xiang Li

и другие.

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

Процитировано

3
Photoinduced N‑Heterocyclic Nitrenium-Catalyzed Single Electron Reduction of α-Chloro Esters for Phenanthridine Synthesis DOI
Ling Zhou,

Xue‐Feng Pei,

Wei Gong

и другие.

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

Процитировано

0
Exploring the Electronic Properties of Cyclic Five-Membered 1,2,3-Triazolium Ions: A Quantum Chemical Study DOI
Kanika Manchanda, N. K. Patra,

Lahu N. Dayare

и другие.

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

Процитировано

0
Visible Light‐Induced N‐Heterocyclic Nitrenium‐Catalyzed Deoxygenative Borylation of Acyl Chlorides DOI Creative Commons

Rahul Mondal,

Apurba Kumar Pal,

K. Geetharani

и другие.

ChemistryEurope, Год журнала: 2025, Номер unknown

Опубликована: Июнь 1, 2025

Considering the appealing synthetic properties of oxygenous feedstocks and organoboron compounds, direct deoxygenative borylation is a very desirable chemical transformation. Directly converting acyl chlorides into alkylboronates through an unknown but valuable reaction. Herein, relatively straightforward one‐step methodology reported where N‐heterocyclic nitrenium (NHN) ion acts as photocatalyst under visible light to produce benzylboronates directly from aroyl in absence metals or additives. A large variety are well tolerated reaction conditions. Mechanistic investigations density functional theory calculations support that NHN species involved radical formation DMAc‐H 2 O/B cat contributes alkylboronates.

Язык: Английский

Процитировано

0
Synthesis and Application of Amino‐1H‐1,2,3‐triazolium Salts DOI

Daiya Kase,

Tsuyoshi Takada,

Nanami Tsuji

и другие.

Asian Journal of Organic Chemistry, Год журнала: 2023, Номер 12(6)

Опубликована: Апрель 22, 2023

Abstract Herein, we developed a fluoride‐mediated nucleophilic aromatic amination of chloro‐1 H ‐1,2,3‐triazolium salts. Various functional groups were tolerated in this reaction, which enabled the synthesis functionalized amino‐1 In addition, investigated catalytic properties triazolium‐based N‐heterocyclic imines (NHIs) for cyanosilylation ketones. The substituent was found to play crucial role inducing high activity.

Язык: Английский

Процитировано

7
N-heterocyclic nitrenium charge transfer catalysis via inner-sphere electron transfer in concert with halogen-atom dissociation DOI
Chaoshen Zhang,

Chang-Zhen Fang,

Yi Liang

и другие.

Organic Chemistry Frontiers, Год журнала: 2023, Номер 11(3), С. 673 - 683

Опубликована: Ноя. 28, 2023

We report an efficient and versatile catalytic N-heterocyclic nitrenium charge transfer complex strategy for the single-electron reduction of chloroform, resulting in generation dichloromethyl radical use various transformations.

Язык: Английский

Процитировано

7
Nitrenium ions as new versatile reagents for electrophilic amination DOI Creative Commons
Idan Avigdori, Kuldeep Singh, Natalia Fridman

и другие.

Chemical Science, Год журнала: 2023, Номер 14(43), С. 12034 - 12040

Опубликована: Янв. 1, 2023

Bench-stable N-heterocyclic nitrenium ions were used for the efficient electrophilic amination of organometallic nucleophiles. The previously unexplored N -alkyl/aryl triazane intermediates reduced to produce a diverse scope primary amines.

Язык: Английский

Процитировано

4
Organocatalyzed iodine-mediated reversible-deactivation radical polymerization via photoinduced charge transfer complex catalysis DOI
Xiang Li, Beibei Zhang, Zhixiang Wang

и другие.

Chinese Chemical Letters, Год журнала: 2024, Номер unknown, С. 110383 - 110383

Опубликована: Авг. 1, 2024

Язык: Английский

Процитировано

1
Stable, aromatic, and electrophilic azepinium ions: Design using quantum chemical methods DOI Open Access
N. K. Patra, Astha Gupta, Prasad V. Bharatam

и другие.

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

Процитировано

1