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

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(43), P. 12034 - 12040

Published: Jan. 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.

Language: Английский

N-Heterocyclic Nitrenium-Catalyzed Photohomolysis of CF3SO2Cl for Alkene Trifluoromethylation DOI

Xiaojian Ren,

Peng-Wei Liao,

Sheng He

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(33), P. 6189 - 6194

Published: Aug. 14, 2023

N-Heterocyclic nitreniums (NHNs) have been utilized as Lewis acid catalysts to activate substrates with lone pairs. Alternative their conventional applications, we discovered that NHNs can also serve charge transfer complex catalysts. Herein, present another potential of by utilizing a weak interaction between and CF3SO2Cl. The method promotes CF3SO2Cl undergo photohomolysis, resulting in the CF3 radical. Mechanistic studies suggested could be due π-hole effect NHNs.

Language: Английский

Citations

14
Benzotriazolium Salts: Emergent Readily Accessible Bench-Stable Lewis Acid Catalysts DOI Creative Commons

Tobias Danelzik,

Sumi Joseph,

Christian Mück‐Lichtenfeld

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(33), P. 6105 - 6110

Published: Aug. 16, 2022

In this work, benzotriazolium salts have been introduced as efficient, readily accessible, bench-stable Lewis acid catalysts. Though these sorts of N-heterocyclic compounds found wide applications ionic liquids or electrolytes, their catalytic activity remained unexplored. Herein, potential catalysts was demonstrated in two prototypical allylic and Nazarov cyclization reactions, showing a matching reactivity allowing low loadings (down to 0.5 mol %).

Language: Английский

Citations

22
Photocatalytic dehydrogenative coupling of silanes with alcohols triggered by light-induced sulfur vacancies on CdS nanosheets DOI
Junhua Zou,

Yiping Wan,

Yidong Hou

et al.

Journal of Catalysis, Journal Year: 2023, Volume and Issue: 428, P. 115154 - 115154

Published: Oct. 1, 2023

Language: Английский

Citations

13
Radical Replacement Process for Ligated Boryl Radical-Mediated Activation of Unactivated Alkyl Chlorides for C(sp3)–C(sp3) Bond Formation DOI Creative Commons

Chang-Zhen Fang,

Beibei Zhang,

Yongliang Tu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 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

Language: Английский

Citations

4
Multimodal Reactivity of N–H Bonds in Triazanes and Isolation of a Triazinyl Radical DOI
Alexander N. Koronatov,

Assaf Mauda,

Boris Tumansky

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(51), P. 23642 - 23648

Published: Dec. 16, 2022

The employment of nitrogen Lewis acids based on nitrenium cations has been increasingly featured in the fields main group chemistry and catalysis. A formally reduced form D─cyclic triazanes E─are intriguing chemical compounds, which is completely unexplored. In this work, we reveal that N–H-triazanes exhibit unusual N–H bond properties; namely, they can serve as protons, hydrides, or hydrogen atom donors. This unique multimodal reactivity provides an N-cation, N-anion, N-radical from same species. It allowed us to isolate, for first time, a stable naphto[1,2,3]triazinyl radical, was fully characterized both computationally experimentally, including its monomeric X-ray structure. Moreover, radical be prepared directly cation by single electron reduction (E = −0.46 V), process reversible. We envision versatile uses synthetic materials chemistry.

Language: Английский

Citations

17
N-Heterocyclic nitrenium-catalyzed photoreductive radical-polar crossover for alkene dicarbofunctionalization DOI Creative Commons

Youfeng Han,

Beibei Zhang, Zhixiang Wang

et al.

Green Synthesis and Catalysis, Journal Year: 2024, Volume and Issue: unknown

Published: March 1, 2024

The photoredox radical-polar crossover paradigm is a valuable tool for 1,2-difunctionalization of alkenes. However, the use unactivated alkyl halides as radical precursors remains far less developed. Here, we report photoreductive N-heterocyclic nitrenium-catalyzed 1,2-dicarbofunctionalization alkenes by using and aryl iodides. These reactions can be carried out under simple, transition-metal-free conditions with easily obtainable materials such alkyl/aryl halides, alkenes, aldehydes. exhibit broad range substrate compatibility good tolerance towards functional groups. This approach offers new to unlock carbon skeletons.

Language: Английский

Citations

3
Development of Modular Nitrenium Bipolar Electrolytes for Possible Applications in Symmetric Redox Flow Batteries DOI
Andrii Varenikov, Mark Gandelman, Matthew S. Sigman

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(28), P. 19474 - 19488

Published: July 4, 2024

Amid the escalating integration of renewable energy sources, demand for grid storage solutions, including non-aqueous organic redox flow batteries (oRFBs), has become ever more pronounced. oRFBs face a primary challenge irreversible capacity loss attributed to crossover redox-active materials between half-cells. A possible solution involves utilization bipolar electrolytes that act as both catholyte and anolyte. Identifying such molecules poses several challenges it requires delicate balance stability oxidation states density, which is influenced by separation two events. We report development diaminotriazolium core capable producing electronically distinct persistent radical species with typically extreme reduction potentials (

Language: Английский

Citations

3
Triazenolysis of alkenes as an aza version of ozonolysis DOI
Alexander N. Koronatov, Pavel А. Sakharov, Deepak Ranolia

et al.

Nature Chemistry, Journal Year: 2024, Volume and Issue: 17(1), P. 101 - 110

Published: Oct. 11, 2024

Language: Английский

Citations

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

Yongliang Tu,

Xiangyu Chen, Xiang Li

et al.

Synthesis, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 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

Language: Английский

Citations

3
Dynamic Covalent Optical Chirality Sensing with a Sterically Encumbered Aminoborane DOI Creative Commons
Zeus A. De los Santos, Ciarán C. Lynch, Christian Wolf

et al.

Chemistry - A European Journal, Journal Year: 2022, Volume and Issue: 28(61)

Published: July 7, 2022

A sterically encumbered aminoborane sensor is introduced and used for quantitative stereochemical analysis of monoalcohols, diols amino alcohols. The small-molecule probe exhibits a rigid ortho-substituted arene scaffold with proximate boron binding site triarylamine circular dichroism (CD) reporter unit which proved to be crucial the observed chiroptical signal induction. Coordination chiral target molecule produces strong Cotton effects UV changes that are readily correlated its absolute configuration, enantiomeric composition concentration achieve comprehensive within 5 % error margin. sensing method was successfully applied in chromatography-free less than one milligram crude asymmetric reaction mixture advantages this approach, amenable high-throughput experimentation equipment automation, over traditional methods discussed.

Language: Английский

Citations

11