Copper Nanoparticles and Copper-Containing Metal-Organic Coordination Polymers in the Catalytic Aminayion of 2-Halopyridines

Dmitry A. Leksakov; Лексаков Дмитрий Александрович; Anastasia S. Borisova; Борисова Анастасия Сергеевна; Arina V. Murashkina; Мурашкина Арина Валерьевна; Daria S. Kulyukhina; Кулюхина Дарья Сергеевна; Alexey D. Averin; Аверин Алексей Дмитриевич; Vadim V. Vergun; Вергун Вадим Вячеславович; Vera I. Isaeva; Исаева Вера Ильинична; Evgeny N. Savelyev; Савельев Евгений Николаевич; Ivan A. Novakov; Новаков Иван Александрович; Irina P. Beletskaya; Белецкая Ирина Петровна

doi:10.31857/S0514749225040011

Copper Nanoparticles and Copper-Containing Metal-Organic Coordination Polymers in the Catalytic Aminayion of 2-Halopyridines

Authors: Leksakov D.A.¹, Borisova A.S.¹, Murashkina A.V.¹, Kulyukhina D.S.¹, Averin A.D.¹^,2, Vergun V.V.³, Isaeva V.I.³, Savelyev E.N.⁴, Novakov I.A.⁴, Beletskaya I.P.¹^,2
Affiliations:
1. Lomonosov Moscow State University
2. Frumkin Institute of Physical Chemistry and Electrochemistry of the RAS
3. Zelinsky Institute of Organic Chemistry of the RAS
4. Volgograd State Technical University
Issue: Vol 61, No 4 (2025)
Pages: 353-363
Section: ЭКСПЕРИМЕНТАЛЬНЫЕ СТАТЬИ
URL: https://stomuniver.ru/0514-7492/article/view/689608
DOI: https://doi.org/10.31857/S0514749225040011
EDN: https://elibrary.ru/SDDCKV
ID: 689608

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Abstract

The efficiency of copper-containing metal-organic coordination polymers (Cu-MOFs) and commercially available non-immobilized copper nanoparticles (CuNPs) in the amination of 2-iodopyridine, 2-bromo-pyridine and its trifluoromethyl derivatives with n-octylamine and adamantane-containing amines with different steric hindrances at the amino group was compared. The yields of the amination products under optimized conditions were shown to be close for both catalytic systems. To achieve good yields in the case of 2-bromopyridine, an increase in the concentration of reagents and the use of 2 equiv. of haloarene are required, while the introduction of a trifluoromethyl group at position 6 of the pyridine ring improves the yields of the amination products. Increasing steric hindrances at the amino group leads to a noticeable decrease in the yields of products in the Cu-MOF catalyzed reactions. However, the use of CuNPs allows for successful reactions with such amines, and CuNPs of 25 nm average size demonstrated an advantage over bifractional nanoparticles of 10/80 nm. On the other hand, increasing the concentration of reagents in the Cu-MOF catalyzed reactions provides good yields of the target compounds without addition ligands.

Keywords

amination, pyridine, haloarenes, amines, adamantane, copper nanoparticles, metal-organic coordination polymers

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