Polyphosphoric Acid Catalyzed C‐H Dinitration of Passivated Aromatic Compounds with Potassium Nitrate under Mild Condition DOI

Yixiong Jia,

Bin Wen,

Peiran Nan

et al.

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 15, 2024

Abstract Dinitroaromatics are valuable organic compounds. However, the high value of these compounds is accompanied by significant risks and formidable challenges. Herein, we report a safe highly efficient method for dinitration various aromatic compounds, using KNO 3 as nitrating agent, polyphosphoric acid solvent catalyst. This approach provides safer more alternative to traditional mixed system, making it suitable range substrates, especially deactivated arenes.

Language: Английский

Structural Insights into the N–N Bond-Formation Mechanism of the Heme-Dependent Piperazate Synthase KtzT DOI

Yunyun Yang,

Yanling Li, Licheng Yao

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(2), P. 1265 - 1273

Published: Jan. 7, 2025

N–N bond formation plays a critical role in the synthesis of organic compounds and has broad applications producing dyes, pharmaceuticals, functional materials. However, is challenging due to nucleophilicity nitrogen. Here, we determined crystal structures heme-dependent enzyme, KtzT, which catalyzes cyclization l-N5-hydroxyornithine (l-N5-OH-Orn) yield l-piperazate (l-piz) by linking two intramolecular nitrogen atoms. The complex structure KtzTC197A with l-N5-OH-Orn reveals substrate-interaction network, validated through mutagenesis experiments. Notably, N5 atom substrate directly coordinates heme iron, precluding oxygen binding. This supports prior knowledge that KtzT an oxygen-independent reaction. Intriguingly, exhibits distinct conformations our crystals. Based on distance between atoms product accommodation pose KtzTC197A/l-piz structure, conformation 2 likely productive pose, while more extended 1 may be transient state facilitating entry into catalytic tunnel. A potential pathway also proposed. These findings offer structural insights for developing bio- metal-catalyzed methods formation.

Language: Английский

Citations

2
Controllable Molecular Editing of 2-Amino-N-substituted Benzamides: Site-selective Synthesis of 6-Selenylated N-Substituted 1,2,3-Benzotriazine-4(3H)-ones DOI

Yatang Wang,

Xiaofeng Hua,

Yinyin Li

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 3, 2025

We present an efficient silver-catalyzed one-pot controllable molecular editing protocol for the transformation of 2-amino-N-substituted benzamides into 6-selenylated N-substituted 1,2,3-benzotriazine-4(3H)-ones under mild reaction conditions. This three-component strategy is achieved by building N-N/N═N/C-Se bonds, which provides a practical pathway preparation selenylated with broad substrate scope and good functional group tolerance, as well high site-selectivity. Mechanistic experiments suggest that this proceeds via intermolecular site-selective C-H selenylation readily available diselenides, followed annulation using AgNO3 nitrogen synthon.

Language: Английский

Citations

0
Mechanochemical Conditions for Intramolecular N–O Couplings via Rhodium Nitrenoids Generated from N‐Acyl Sulfonimidamides DOI Creative Commons

Shulei Pan,

Peng Wu,

Dimitra Bampi

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 9, 2024

Abstract Starting from N ‐acyl sulfonimidamides, mechanochemically generated rhodium nitrenoids undergo intramolecular N−O couplings to provide unprecedented 1,3,2,4‐oxathiadiazole 3‐oxides in good excellent yields. The cyclization proceeds efficiently with a catalyst loading of only 0.5 mol % the presence phenyliodine(III) diacetate (PIDA) as oxidant. Neither an inert atmosphere nor additional heating is required this solvent‐free procedure. Under heat or blue light, newly formed five‐membered heterocycles function nitrene precursors reacting sulfoxides exemplified by imidation dimethyl sulfoxide.

Language: Английский

Citations

2
Photo- and Electro-chemical Strategies for Indazole Synthesis DOI Creative Commons
Binbin Huang

Tetrahedron Chem, Journal Year: 2024, Volume and Issue: unknown, P. 100116 - 100116

Published: Dec. 1, 2024

The indazole core is prevalently found in the structures of bioactive molecules, demonstrating promising potential medicinal chemistry and drug discovery, which therefore has attracted sustained attention from synthetic community. Over recent decades, significant progress been achieved both organic photocatalysis electrosynthesis, offering novel approaches for efficient sustainable synthesis various functionalized indazoles. This mini-review highlights emerging methodological advancements photo-/electro-chemical two common forms indazole, namely 1H- 2H-indazoles, are classified by specific intramolecular bond formation patterns: (1) C-C formation, (2) C-N (3) N-N formation. reaction conditions, representative scopes, mechanistic understandings these protocols emphasized, to elucidate advantages limitations current strategies, with an aim inspire future innovations that may address challenges modern synthesis.Graphical abstractTo create your abstract, type over instructions template box below. Fonts or abstract dimensions should not be changed altered.

Language: Английский

Citations

1
Recent Developments and Challenges in the Enzymatic Formation of Nitrogen–Nitrogen Bonds DOI Creative Commons

Charitomeni Angeli,

Sara Atienza-Sanz, Simon Schröder

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 15(1), P. 310 - 342

Published: Dec. 17, 2024

The biological formation of nitrogen–nitrogen (N–N) bonds represents intriguing reactions that have attracted much attention in the past decade. This interest has led to an increasing number N–N bond-containing natural products (NPs) and related enzymes catalyze their (referred this review as NNzymes) being elucidated studied greater detail. While more detailed information on biosynthesis NPs, which only become available recent years, provides unprecedented source biosynthetic enzymes, potential for biocatalytic applications been minimally explored. With review, we aim not provide a comprehensive overview both characterized NNzymes hypothetical biocatalysts with putative bond forming activity, but also highlight from perspective. We present compare conventional synthetic approaches linear cyclic hydrazines, hydrazides, diazo- nitroso-groups, triazenes, triazoles allow comparison enzymatic routes via these functional groups. Moreover, pathways well diversity reaction mechanisms are presented according direct groups currently accessible enzymes.

Language: Английский

Citations

1
Mechanochemical Conditions for Intramolecular N–O Couplings via Rhodium Nitrenoids Generated from N‐Acyl Sulfonimidamides DOI Creative Commons

Shulei Pan,

Peng Wu,

Dimitra Bampi

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 9, 2024

Abstract Starting from N ‐acyl sulfonimidamides, mechanochemically generated rhodium nitrenoids undergo intramolecular N−O couplings to provide unprecedented 1,3,2,4‐oxathiadiazole 3‐oxides in good excellent yields. The cyclization proceeds efficiently with a catalyst loading of only 0.5 mol % the presence phenyliodine(III) diacetate (PIDA) as oxidant. Neither an inert atmosphere nor additional heating is required this solvent‐free procedure. Under heat or blue light, newly formed five‐membered heterocycles function nitrene precursors reacting sulfoxides exemplified by imidation dimethyl sulfoxide.

Language: Английский

Citations

0
Synthesis of 1,3,5-Trisubstituted 1,2,4-Triazoles Enabled by a Gold-Catalyzed Three-Component Reaction DOI
Howard Díaz‐Salazar,

Carlos M. Ramírez-González,

Miguel A. Rosas-Ortega

et al.

Tetrahedron, Journal Year: 2024, Volume and Issue: 168, P. 134358 - 134358

Published: Nov. 3, 2024

Language: Английский

Citations

0
Polyphosphoric Acid Catalyzed C‐H Dinitration of Passivated Aromatic Compounds with Potassium Nitrate under Mild Condition DOI

Yixiong Jia,

Bin Wen,

Peiran Nan

et al.

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 15, 2024

Abstract Dinitroaromatics are valuable organic compounds. However, the high value of these compounds is accompanied by significant risks and formidable challenges. Herein, we report a safe highly efficient method for dinitration various aromatic compounds, using KNO 3 as nitrating agent, polyphosphoric acid solvent catalyst. This approach provides safer more alternative to traditional mixed system, making it suitable range substrates, especially deactivated arenes.

Language: Английский

Citations

0