Eco-Efficient, Green, and Scalable Synthesis of 1,2,3-Triazoles Catalyzed by Cu(I) Catalyst on Waste Oyster Shell Powders

Abstract

An efficient and recyclable waste oyster shell powders (OSPs)-supported CuBr catalyst (OSPs–CuBr) has been successfully prepared and well characterized by Fourier transform infrared (FTIR) spectroscopy, thermal gravimetric analysis (TGA), atomic absorption spectroscopy (AAS), and powder X-ray diffraction (XRD). Then, OSPs–CuBr was used as a heterogeneous catalyst for the one-pot multicomponent synthesis of 1,4-disubstituted 1,2,3-triazole derivatives via a Cu­(I)-catalyzed azide–alkyne 1,3-dipolar cycloaddition (CuAAC) reaction. Compared with a CaCO3–CuBr catalyst, the OSPs–CuBr catalyst showed higher catalytic activity and stability characteristics. The chitin and protein molecules on the OSP particles surfaces play an important role in the chelation of the CuBr species, which leads to the better chemical stability of OSPs–CuBr. The 1,2,3-triazoles are readily obtained in good to excellent yields and on a multigram scale by the reaction of aryl/alkyl halides, alkynes, and NaN3 under microwave irradiation conditions. It also showed good reusability, could be easily recovered through filtration and washing, and was reused at least eight times with virtually no evident loss of catalytic performance.

Sol–gel entrapped Cu in a silica matrix: An efficient heterogeneous nanocatalyst for Huisgen and Ullmann intramolecular coupling reactions

“…Furthermore, alkyl azides generally have boiling points similar to those of the corresponding alkyl bromides. Thus, we decided to initiate a systematic study of the versatility of the nucleophilic substitution of the halide using NaN 3 [52][53][54][55][56][57][58][59][60][61] in t-BuOH/H 2 O at room temperature ( Table 2). The initial exploration was aimed at the direct synthesis of 1,2,3-triazoles 3 and the reaction of benzyl bromide, sodium azide and phenylacetylene in the presence of TEA was chosen as a model transformation.…”

Magnetic γFe2O3@Sh@Cu2O: an efficient solid-phase catalyst for reducing agent and base-free click synthesis of 1,4-disubstituted-1,2,3-triazoles

“…The reaction is done by adding a large excess of copper to the azide/alkyne mixture. Until now, the Huisgen's copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) remain the most popular reaction making possible to rapidly, quantitatively, and reproducibly obtain a large variety of fivemembered heterocycles via heteroatomic bonds [1][2][3][4][5][6][7][8][9][10][11][12]. However, the classical conditions of Huisgen reaction necessitates elevated temperatures, prolonged reaction times and lead to a mixture of isomeric 1,4-and 1,5-triazoles ( Fig.…”

“…To overcome the difficulty of catalyst separation, some heterogeneous catalyst have been made such as copper(I)-modified SiO 2 [4], nano ferrite-glutathionecopper (nano-FGT-Cu) [5], amberlyst A-21-copper(1) [6], Cu nano particles supported on agarose [7], Cu(I) on waste oyster shell powder [8], copper nanoparticles on charcoal [9], copper nanoparticles on activated carbon [1], Cu(I) supported on alumina (Cu/Al 2 O 3 ) [1], copper immobilized onto a triazole functionalized magnetic nanoparticle [19], cellulose supported cuprous iodide nano particles [20], polymer supported copper [21], magnetic copper starch nanocomposite [22], knitted N-heterocyclic carbene-copper complex [23,24], copper(I)-phosphinite complex [25], Fe 3 O 4 nanoparticle-supported Cu(II)-β-cyclodextrin complex [26], Cu@ PyIm-SBA-15 [27], Ag-Al 2 O 3 @Fe 2 O 3 [28], and hierarchical mesoporous organic polymer Cu-HMOP [29] for the synthesis of 1,2,3-triazoles. Despite these achievements some of these heterogeneous catalyst have significant limitations such as using reducing agent to reduce Cu(II) to Cu(I), lack of regioselectivity, by-product production, high temperature, long reaction time, and difficult conditions.…”

Functionalized expanded corn starch‐anchored Cu(I): An efficient and recyclable catalyst for oxidation of 5‐hydroxymethylfurfural to 2,5‐diformylfuran

“…In recent years, low-cost and green synthesis of supported catalysts from biomass has attracted growing interest. [18,19] In continuation of our efforts to develop green, highly efficient and practical chemical methods as well as a focus on the application of biomass-based heterogeneous catalysts in organic reactions, [20] we identified that Schiff base-functionalized expanded corn starch-supported CuBr (ECS-SB-CuBr) in the presence of TEMPO as a co-catalyst was an efficient catalyst for promoting the selective aerobic oxidation of HMF into DFF under ambient pressure of dioxygen at 50 C in acetonitrile (Scheme 1). In addition, the catalyst is stable to air and moisture and can be easily recovered and reused.…”