Copper(I)‐N2S2‐salen type complex covalently anchored onto MCM‐41 silica: an efficient and reusable catalyst for the A3‐coupling reaction toward propargylamines
Copper(I)‐N2S2‐salen type complex covalently anchored onto MCM‐41 silica: an efficient and reusable catalyst for the A3‐coupling reaction toward propargylamines
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共价锚定在 MCM-41 二氧化硅上的铜（I）-N2S2-salen 型络合物：一种高效且可重复使用的炔丙胺 A3 偶联反应催化剂
DOI：
10.1002/aoc.2976
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发表时间：
2013
影响因子：
3.9
通讯作者：
Mohsen Moradian
中科院分区：
文献类型：
--
作者：
H. Naeimi;Mohsen Moradian
本文报道了铜配合物在介孔分子筛MCM-41表面的共价锚定。以卤化铜为配体，将双[2-（苯硫基）亚苄基]-1，2-乙二胺作为一种新的N2S2给体salen型配体共价锚定在MCM-41的纳米孔上。以3-巯丙基三甲氧基硅烷为活性表面改性剂，制备了有机-无机杂化材料。2-硝基苯甲醛与硫醇部分顺利反应，以形成具有甲醛基团的官能化纳米多孔二氧化硅。将所得的负载有机部分转化为thisalen配体并与CuX（X = CN，Cl，Br，I）配位。通过X-射线衍射、N2吸附、FT-IR、漫反射紫外可见和TGA技术表征的多相催化剂表明，成功地将铜络合物接枝到MCM-41的纳米通道内。通过醛、胺和炔的Mannich缩合反应对多相化催化剂进行了评价。在该反应中，以良好至优异的产率获得相应的炔丙胺作为单一产物。讨论了反应温度、溶剂、催化剂负载量、催化剂的浸取和重复使用等因素对反应的影响。使用MCM-41作为载体允许更容易的分离和循环，反应性仅略微降低。版权所有© 2013约翰威利父子有限公司.
The immobilization of copper complexes by covalent anchoring of the ligand on the surface of mesoporous MCM-41 has been described. Bis[2-(phenylthio)benzylidene]-1,2-ethylenediamine as a new N2S2 donor salen-type ligand was covalently anchored onto nanopores of MCM-41 coordinated with copper (I) halide. The organic–inorganic hybrid material was achieved readily using 3-mercaptopropyltrimethoxysilane as a reactive surface modifier. 2-Nitrobenzaldehyde was reacted smoothly with the thiol moieties in order to form functionalized nanoporous silica with carbaldehyde groups. The resulting supported organic moieties were converted to thiosalen ligand and coordinated with CuX (X = CN, Cl, Br, I). Characterization of the heterogeneous catalyst by X-ray diffraction, N2 sorption, FT-IR, diffuse reflectance UV-visible and TGA techniques indicated successful grafting of the copper complex inside the nano-channels of MCM-41. The heterogenized catalyst was evaluated by the Mannich condensation reaction of aldehydes, amines and alkynes. In this reaction, the corresponding propargylamines were obtained as single products in good to excellent yields. Factors such as reaction temperature, solvent, catalyst loading, leaching and reusability of the catalyst also were discussed. The use of MCM-41 as support permits an easier separation and recycles with only a marginal decrease in reactivity. Copyright © 2013 John Wiley & Sons, Ltd.