Iron Single-Atom Catalyzed N-Alkylation of Amines with Alcohols via Solvent-Free Borrowing Hydrogen Strategy

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61989592%3A15640%2F25%3A73632937" target="_blank" >RIV/61989592:15640/25:73632937 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61989100:27640/25:10258725

Výsledek na webu

<a href="https://advanced.onlinelibrary.wiley.com/doi/10.1002/advs.202507915" target="_blank" >https://advanced.onlinelibrary.wiley.com/doi/10.1002/advs.202507915</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/advs.202507915" target="_blank" >10.1002/advs.202507915</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Iron Single-Atom Catalyzed N-Alkylation of Amines with Alcohols via Solvent-Free Borrowing Hydrogen Strategy

Popis výsledku v původním jazyce

Industrial hydrogenation is a pivotal process in chemical synthesis. However, it has significant drawbacks, including high cost, safety risks associated with the use of molecular hydrogen gas, and substantial energy demands due to the need for elevated temperatures and pressures to achieve satisfactory yields. The borrowing hydrogen synthesis, which enables the transfer of hydrogen between molecules, offers a promising approach for green, one-pot synthesis of industrially important chemicals and intermediates. Despite its potential, the broad application remains limited due to the reliance on toxic solvents, expensive noble metal catalysts, and the still restricted efficiency and substrate scope. In this study, the first solvent-free strategy for the N-alkylation of amines with alcohols is presented, employing an N-doped graphene-supported Fe single-atom catalyst (FeSA@N-G; 1.06 wt.%). This approach achieves superior conversion and selectivity (up to 99%) along with record values for turnover number (TON, 1032.7) and turnover frequency (TOF, 413.1 h-1) for the coupling reaction of aniline with benzyl alcohol, surpassing all previously reported catalysts. DFT calculations, combined with experimental data, elucidated the reaction mechanism and identified the Fe1(III)-N4 active site participating in Fe-H hydride transfer and containing two pyrrolic and two pyridinic nitrogens bound to the Fe center. The developed technology is further supported by the catalyst&apos;s excellent scalability, reusability, and performance under continuous-flow conditions. Additionally, the exceptional efficiency of the single-atom catalyst is demonstrated across more than 50 substrates, including reactions involving both aliphatic and aromatic amines with aliphatic and aromatic alcohols. The industrial applicability of this technology is validated through the synthesis of pharmaceutically relevant compounds, including stimulant drugs, antihistamines, and pharmaceutical intermediates.

Název v anglickém jazyce

Iron Single-Atom Catalyzed N-Alkylation of Amines with Alcohols via Solvent-Free Borrowing Hydrogen Strategy

Popis výsledku anglicky

Industrial hydrogenation is a pivotal process in chemical synthesis. However, it has significant drawbacks, including high cost, safety risks associated with the use of molecular hydrogen gas, and substantial energy demands due to the need for elevated temperatures and pressures to achieve satisfactory yields. The borrowing hydrogen synthesis, which enables the transfer of hydrogen between molecules, offers a promising approach for green, one-pot synthesis of industrially important chemicals and intermediates. Despite its potential, the broad application remains limited due to the reliance on toxic solvents, expensive noble metal catalysts, and the still restricted efficiency and substrate scope. In this study, the first solvent-free strategy for the N-alkylation of amines with alcohols is presented, employing an N-doped graphene-supported Fe single-atom catalyst (FeSA@N-G; 1.06 wt.%). This approach achieves superior conversion and selectivity (up to 99%) along with record values for turnover number (TON, 1032.7) and turnover frequency (TOF, 413.1 h-1) for the coupling reaction of aniline with benzyl alcohol, surpassing all previously reported catalysts. DFT calculations, combined with experimental data, elucidated the reaction mechanism and identified the Fe1(III)-N4 active site participating in Fe-H hydride transfer and containing two pyrrolic and two pyridinic nitrogens bound to the Fe center. The developed technology is further supported by the catalyst&apos;s excellent scalability, reusability, and performance under continuous-flow conditions. Additionally, the exceptional efficiency of the single-atom catalyst is demonstrated across more than 50 substrates, including reactions involving both aliphatic and aromatic amines with aliphatic and aromatic alcohols. The industrial applicability of this technology is validated through the synthesis of pharmaceutically relevant compounds, including stimulant drugs, antihistamines, and pharmaceutical intermediates.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/EH22_008%2F0004587" target="_blank" >EH22_008/0004587: Technologie za hranicí nanosvěta</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2025

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Advanced Science

ISSN

2198-3844

e-ISSN

—

Svazek periodika

12

Číslo periodika v rámci svazku

46

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

14

Strana od-do

nestránkováno

Kód UT WoS článku

001552070400001

EID výsledku v databázi Scopus

2-s2.0-105013652620