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

Recent advances in the chemistry of isolable carbene analogues with group 13–15 elements DOI
Mian He, Chaopeng Hu, Rui Wei

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(8), P. 3896 - 3951

Published: Jan. 1, 2024

This review provides an overview of main group carbene analogues, covering recent advancements, synthesis strategies, and the diverse reactivity elements in groups 13–15 based on their structural characteristics.

Language: Английский

Citations

32
Advances in CO2 activation by frustrated Lewis pairs: from stoichiometric to catalytic reactions DOI Creative Commons
Md. Nasim Khan, Yara van Ingen,

Tribani Boruah

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(47), P. 13661 - 13695

Published: Jan. 1, 2023

Frustrated Lewis pair systems have been explored efficiently in homogeneous and heterogeneous conditions for the activation reduction of CO 2 to various useful products stoichiometric as well catalytic reactions.

Language: Английский

Citations

33
Unveiling N-Fused Nitreniums as Potent Catalytic Photooxidants DOI

Samim Sohel Rana,

Joyanta Choudhury

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(6), P. 3603 - 3608

Published: Jan. 31, 2024

The first example of a hitherto-unknown facet catalytic photooxidant capability nitrenium cations is reported herein. fundamental limitation inability the traditional and nitreniums to achieve excited-state redox potential beyond +2.0 V (vs Ag/AgCl), primary requirement for powerful photooxidant, addressed in this work by developing structurally unique class N-fused cations, with required structural engineering involving extensive π-conjugation through ring fusion at site, which enabled significant lowering LUMO energy easy reduction excited state (excited-state up +2.5 vs facilitated effective delocalization/stabilization generated radical. This finding opens new way discover novel useful (photo)catalytic properties just Lewis acidity.

Language: Английский

Citations

10
Quantification of photocatalytically-generated hydrogen peroxide in the presence of organic electron donors: Interference and reliability considerations DOI Creative Commons
Yan Wei,

Jingzhen Zhang,

Qian Zheng

et al.

Chemosphere, Journal Year: 2021, Volume and Issue: 279, P. 130556 - 130556

Published: April 13, 2021

Language: Английский

Citations

52
N-Heterocyclic Nitreniums Can Be Employed as Photoredox Catalysts for the Single-Electron Reduction of Aryl Halides DOI

Kun‐Quan Chen,

Beibei Zhang, Zhixiang Wang

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(25), P. 4598 - 4602

Published: June 16, 2022

N-Heterocyclic nitrenium (NHN) salts, the analogues of N-heterocyclic carbenes, have attracted considerable interest. However, relatively little is known about their catalytic ability beyond Lewis acid catalysis. Herein, we describe that NHNs can serve as electron acceptors for charge transfer complex photoactivations. We showcase that, under blue light irradiation, NHN salts could catalyze generation aryl radicals from halides.

Language: Английский

Citations

30
Ligand‐Promoted Iron‐Catalyzed Nitrene Transfer for the Synthesis of Hydrazines and Triazanes through N‐Amidation of Arylamines DOI
Shiyang Zhu, Wen‐Ji He,

G.-J. Shen

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(2)

Published: Nov. 24, 2023

Abstract Herein, we report that bulky alkylphosphines such as P t Bu 3 can switch the roles from actor to spectator ligands promote FeCl 2 ‐catalyzed N ‐amidation reaction of arylamines with dioxazolones, giving hydrazides in high efficiency and chemoselectivity. Mechanistic studies indicated phosphine could facilitate decarboxylation dioxazolones on Fe center, hydrogen bonding interactions between nitrenoid intermediates might play a role modulating delicate interplay ligand, arylamine, acyl nitrene N, favoring N−N coupling over N−P coupling. The new ligand‐promoted protocols offer convenient way access various challenging triazane compounds via double or sequential primary arylamines.

Language: Английский

Citations

19
Homogeneous and Heterogeneous Frustrated Lewis Pairs for the Activation and Transformation of CO2 DOI
Tao Du, Peng Zhang, Zhen Jiao

et al.

Chemistry - An Asian Journal, Journal Year: 2024, Volume and Issue: 19(12)

Published: April 12, 2024

Due to the serious ecological problems caused by high CO

Language: Английский

Citations

7
New Generation of Nitrenium Salts: Catalytic Hydrosilylation of Imines and a Mechanism of Action of Nitrogen Lewis Acids DOI
Kuldeep Singh, Idan Avigdori,

Alexander Kaushansky

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(12), P. 6831 - 6839

Published: May 25, 2022

Nitrogen Lewis acids (NLAs) are emerging as a powerful tool in strong bond activation and catalysis. Till now, N,N-dialkyl-nitrenium salts were known utilized chemical transformations. In this article, we report on the synthesis characterization of next generation nitrenium-based acids─N,N-diaryl-substituted naphthotriazinium salts─,which opens door to libraries stereoelectronically modifiable catalysts. We exemplify potency these acidic catalysts gram-scale hydrosilylation various ketimines aldimines yields up 99% catalyst loading low 0.1 mol %. Notably, dialkyl-nitrenium proved inefficient reaction. Based our experimental theoretical studies, elucidated mechanistic action nitrenium such reduction-type reactions, demonstrating unique hydridic behavior N–H bonds triazanes.

Language: Английский

Citations

27
Triazolium Salts as Lewis Acid Catalysts DOI
Deepak Ranolia, Idan Avigdori, Kuldeep Singh

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(22), P. 3915 - 3919

Published: May 26, 2022

We describe a new type of nitrenium-based Lewis acids: tetraaryl-1,2,3-triazolium salts. These were fully characterized by NMR and X-ray crystallography. The Gutmann-Beckett acidity numbers determined to be up 35.6, which is high compared those previously studied nitrenium salts catalyze the facile hydrosilylation-deoxygenation ketones, aldehydes, acetals, alcohols, ethers, silyl ethers under mild conditions in excellent yields. To our knowledge, this represents first example triazolium ions used as acid catalysts.

Language: Английский

Citations

23
Additive free, N-heterocyclic nitrenium catalyzed photoreduction of cycloketone oxime esters DOI
Xiao-Di Su,

Zhusheng Yang,

Wei Gong

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(5), P. 1160 - 1165

Published: Jan. 1, 2023

N-Heterocyclic nitrenium iodide salts can be used as ideal charge transfer complex catalysts for the photoreduction of cycloketone oxime esters.

Language: Английский

Citations

16