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

ACS Catalysis, Год журнала: 2025, Номер 15(2), С. 1265 - 1273

Опубликована: Янв. 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.

Язык: Английский

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Ligand‐Promoted Iron‐Catalyzed Nitrene Transfer for the Synthesis of Hydrazines and Triazanes through N‐Amidation of Arylamines

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(2)

Опубликована: Ноя. 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.

Язык: Английский

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Recent Advances in Catalytic Nitrogen–Nitrogen Bond Formation Reactions

ACS Catalysis, Год журнала: 2024, Номер 14(8), С. 5735 - 5778

Опубликована: Апрель 1, 2024

The lack of effective strategies for direct construction nitrogen–nitrogen bonds has hampered developments in the synthesis and application molecules containing hydrazine or azo motifs. Attracted by their properties both material science medicinal chemistry, more attention been drawn to this area, resulting fast growth design azaheterocycles substituted hydrazines. This review focuses on efficient catalytic approaches toward formation N–N N═N through different strategies, including oxidative dehydrogenation, nitrene-transfer reaction, reductive coupling, some other recently developed methods.

Язык: Английский

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Photoinduced Difunctionalization of Diazenes Enabled by N–N Radical Coupling

Organic Letters, Год журнала: 2023, Номер 25(36), С. 6671 - 6676

Опубликована: Авг. 29, 2023

In this study, a metal-free difunctionalization strategy for diazenes was developed using range of bifunctionalization reagents. This involves unique N(sp3)–N(sp2) radical coupling between the hydrazine and imine radical. More than 30 triazane core motifs were constructed by installing imines various functional groups, including alkyl, phenyl, cyanoalkyl, sulfonyl on both ends nitrogen–nitrogen bond in an efficient manner.

Язык: Английский

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Discovery of a Bacterial Hydrazine Transferase That Constructs the N-Aminolactam Pharmacophore in Albofungin Biosynthesis

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(19), С. 13399 - 13405

Опубликована: Май 3, 2024

Structural motifs containing nitrogen-nitrogen (N-N) bonds are prevalent in a large number of clinical drugs and bioactive natural products. Hydrazine (N

Язык: Английский

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Extending GPU-accelerated Gaussian integrals in the TeraChem software package to f type orbitals: Implementation and applications

The Journal of Chemical Physics, Год журнала: 2024, Номер 161(17)

Опубликована: Ноя. 6, 2024

The increasing availability of graphics processing units (GPUs) for scientific computing has prompted interest in accelerating quantum chemical calculations through their use. However, the complexity integral kernels high angular momentum basis functions often limits utility GPU implementations with large sets or metal containing systems. In this work, we report implementation f function support GPU-accelerated TeraChem software package development efficient evaluation Hamiltonian integrals. efficiency resulting code is demonstrated density functional theory (DFT) on increasingly organic molecules and transition complexes, as well coupled cluster singles doubles water clusters. Preliminary investigations into Ni(I) catalysis DFT photochemistry MnH(CH3) complete active space self-consistent field are also carried out. Overall, our appears to be well-suited fast simulation systems, molecules.

Язык: Английский

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Photoredox-Catalyzed Hydroacylation of Azobenzenes with Carboxylic Acids

Organic Letters, Год журнала: 2024, Номер 26(7), С. 1517 - 1521

Опубликована: Фев. 12, 2024

Acyl hydrazides are widely found in bioactive compounds and have important applications as versatile synthetic intermediates. In the current report, a photoredox-catalyzed hydroacylation of azobenzenes was disclosed with carboxylic acids acylation reagent, affording variety N,N′-disubstituted hydrazides. The process possesses advantages mild reaction conditions, broad substrate scope, high efficiency. Preliminary mechanistic investigation indicated that addition an acyl radical to azo compound should be involved.

Язык: Английский

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An SN2 Reaction at Amide Nitrogen Enables Hydrazide Synthesis

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(14)

Опубликована: Фев. 17, 2024

Nucleophilic substitutions are fundamentally important transformations in synthetic organic chemistry. Despite the substantial advances bimolecular nucleophilic (S

Язык: Английский

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An iron-catalyzed nitrene transfer reaction of nitrosobenzenes with N-acyloxyamides for accessing N-acyl azoxy molecules

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(9), С. 2561 - 2565

Опубликована: Янв. 1, 2024

A nitrene transfer reaction of nitrosobenzenes with N -acyloxyamides using FeCl 2 ·4H O as a cheap and commercially available catalyst was developed for facile synthesis -acyl azoxy compounds high functional-group compatibility.

Язык: Английский

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Photoelectrochemical Ni-catalyzed cross-coupling of aryl bromides with amine at ultra-low potential

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Авг. 12, 2024

Photoelectrochemical (PEC) cell is an ideal platform for organic transformation because of its green benefits and minimal energy consumption. As emerging methodology, the reaction types photoelectrocatalytic synthesis (PECOS) are limited to simple oxidation C–H activation at current stage. Metal catalysis construction C(sp2)–N bonds has not been touched yet in PECOS. We introduce here a PEC method that successfully engages Ni mild production aniline derivatives. Experimental computational investigations elucidate addition photoanode-generated amine radical catalyst avoids sluggish nucleophilic attack, enabling proceed ultra-low potential (–0.4 V vs. Ag/AgNO3) preventing overoxidation products conventional electrochemical synthesis. This synergistic strategy exhibits good functional group tolerance wide substrate scope on both aryl halides amines, by which some important natural pharmaceutical chemicals have modified. The stage while metal remains unexplored. Here, authors

Язык: Английский

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