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铜铁氧体@二氧化硅@氧化锆/硫酸根/铜纳米颗粒:一种用于水中无配体和无钯的Sonogashira交叉偶联反应的高效磁可回收多功能路易斯/布朗斯特酸纳米催化剂。

The CuFeO@SiO@ZrO/SO /Cu nanoparticles: an efficient magnetically recyclable multifunctional Lewis/Brønsted acid nanocatalyst for the ligand- and Pd-free Sonogashira cross-coupling reaction in water.

作者信息

Nasseri Mohammad Ali, Alavi Seyyedeh Ameneh, Kazemnejadi Milad, Allahresani Ali

机构信息

Department of Chemistry, Faculty of Science, University of Birjand P. O. Box 97175-615 Birjand Iran

出版信息

RSC Adv. 2019 Jul 3;9(36):20749-20759. doi: 10.1039/c9ra03406d. eCollection 2019 Jul 1.

Abstract

Herein, the synthesis and application of copper-incorporated sulfated zirconium oxide supported on CuFeO NPs (CuFeO@SiO@ZrO/SO /Cu NPs) as a novel Lewis/Brønsted acid nanocatalyst were studied for the Sonogashira C-C cross-coupling reaction. The fabricated CuFeO@SiO@ZrO/SO /Cu catalyst exhibited efficient activity for a large variety of aryl iodides/bromides and, most importantly, aryl chlorides in water and in the presence of NaOH as a base in short reaction times. The catalyst was fully characterized by FTIR, TG-DTG, VSM, XRD, EDX, FE-SEM and TEM analyses. A synergetic effect could be considered to have arisen from the various Lewis acid and Brønsted acid sites present in the catalyst. The efficient incorporation of copper into zirconia provided a robust highly stable hybrid, which prevented any metal leaching, whether from the magnetite moiety and/or Cu sites in the reaction mixture. Moreover, the catalyst was successfully recovered from the mixture by a simple external magnet and reused for at least 9 consecutive runs. Zero metal leaching, stability, consistency with a variety of substrates, fast performance, cost-effectiveness, environmental friendliness, and preparation with accessible and cheap materials are some of the advantages and highlights of the current protocol.

摘要

本文研究了负载在CuFeO纳米颗粒上的铜掺杂硫酸化氧化锆(CuFeO@SiO@ZrO/SO₄²⁻/Cu NPs)作为一种新型Lewis/Brønsted酸纳米催化剂在Sonogashira C-C交叉偶联反应中的合成与应用。制备的CuFeO@SiO@ZrO/SO₄²⁻/Cu催化剂对多种芳基碘化物/溴化物,最重要的是对芳基氯化物,在水中且以NaOH作为碱存在的情况下,在短反应时间内表现出高效活性。通过FTIR、TG-DTG、VSM、XRD、EDX、FE-SEM和TEM分析对催化剂进行了全面表征。可以认为协同效应源于催化剂中存在的各种Lewis酸和Brønsted酸位点。铜有效掺入氧化锆中形成了一种坚固的高度稳定的杂化物,可防止反应混合物中任何金属的浸出,无论是来自磁铁矿部分还是Cu位点。此外,通过简单的外部磁铁可成功从混合物中回收催化剂,并至少连续重复使用9次。零金属浸出、稳定性、与多种底物的一致性、快速性能、成本效益、环境友好性以及使用易得且廉价的材料制备是当前方案的一些优点和亮点。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2880/9065763/21f1818cac43/c9ra03406d-s1.jpg

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