Cu(I)‐anchored polyvinyl alcohol coated‐magnetic nanoparticles as heterogeneous nanocatalyst in Ullmann‐type C–N coupling reactions

Abstract

In this paper, the preparation of a novel magnetic nanocatalyst (Fe3O4@PVA/CuCl) is described, which involves coating of polyvinyl alcohol (PVA) onto the surface of Fe3O4 nanoparticles and its subsequent coordination with CuCl catalyst. The nanocatalyst was characterized by various analytical methods, including Fourier‐transform infrared, X‐ray diffraction, inductively coupled plasma spectroscopy, field emission scanning electron microscopy, energy‐dispersive X‐ray spectroscopy (EDX), transmission electron microscopy, vibrating‐sample magnetometry, and EDX elemental mapping. Moreover, the nanocatalyst was efficiently used in the N‐arylation of amines via the formation of a carbon–nitrogen bond between the aryl halides and amines by Ullmann‐type coupling reactions. The catalyst was sufficiently stable and can be reused for at least seven times in a model Ullmann reaction without remarkable alteration in its catalytic behavior. Heterogeneity of the catalyst was investigated by a hot filtration test.

Synthesis of 9‐O‐Arylated Berberine with a Polystyrene Resin Supported Copper(II) Catalyst

“…To explore the heterogeneity of the PSAPA⋅Cu(II) catalyst, the catalyst was filtered off while hot at 1 h when the arylated product yield was 22% [26] . K 2 CO 3 was added to the filtrate and the mixture was reacted for another 47 h. The solid catalyst removal significantly deteriorated the catalytic process afterwards, and only a slight yield increase to 41 % was noted, while that of the normal catalysis was 99 %.…”

Recent advances in the application of nanocatalysts in C‐N coupling reactions

“…Preparation of Fe 3 O 4 @PVA/CuCl. Reprinted with permission from ref Hemmati et al [ 163 ] Copyright 2020 John Wiley and Sons…”

“…In the same year, Maleki and co-workers [162] demonstrated that CTSN/Fe 3 O 4 -Cu nanocomposite could be used as an inexpensive magnetic nanocatalyst for the N-arylation of imidazoles. This nanocatalyst was synthesized by dropwise addition of copper (II) acetate aqueous solution to a dispersed aqueous mixture of chitosan/Fe 3 O 4 and subsequent sonication for 1 h, at 80 C. [163] Copyright 2020 John Wiley and Sons S C H E M E 3 3 Ullmann cross-coupling reactions catalyzed by Fe 3 O 4 @PVA/CuCl…”

“…Yousefi et al [163] prepared Fe 3 O 4 @PVA/CuCl by coating polyvinyl alcohol onto the surfaces of Fe 3 O 4 NPs, followed by coordination with CuCl (Figure 14). The catalytic behavior of this novel magnetic nanocatalyst was tested in the Ullmann C-N cross-coupling of aryl T A B L E 9 N-arylation reaction of amines with aryl halides using Cu-HB@AS-MNPs F I G U R E 1 5 Preparation of Cu-HB@AS-MNPs.…”

Gold‐Catalyzed Amination Reactions: Progress and Prospects

“…Coupling reaction has emerged as a powerful tool to access carbon‐carbon and carbon‐heteroatom bonds [1,2,3] . Transition‐metal‐catalyzed coupling reactions have achieved rapid progress in recent times.…”