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

Result code in 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>

Alternative codes found

RIV/61989100:27640/25:10258725

Result on the web

<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>

Result language

angličtina

Original language name

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

Original language description

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.

Czech name

—

Czech description

—

Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

—

OECD FORD branch

10403 - Physical chemistry

Project

<a href="/en/project/EH22_008%2F0004587" target="_blank" >EH22_008/0004587: Technology Beyond Nanoscale</a><br>

Continuities

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

Publication year

2025

Confidentiality

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

Name of the periodical

Advanced Science

ISSN

2198-3844

e-ISSN

—

Volume of the periodical

12

Issue of the periodical within the volume

46

Country of publishing house

US - UNITED STATES

Number of pages

14

Pages from-to

nestránkováno

UT code for WoS article

001552070400001

EID of the result in the Scopus database

2-s2.0-105013652620