Aguirre-Díaz Lina María, Iglesias Marta, Snejko Natalia, Gutiérrez-Puebla Enrique, Monge M Ángeles
Departamento de Nuevas Arquitecturas en Química de Materiales, Instituto de Ciencia de Materiales de Madrid (ICMM-CSIC), Sor Juana Inés de la Cruz 3, Cantoblanco, 28049, Madrid, Spain.
Chemistry. 2016 May 4;22(19):6654-65. doi: 10.1002/chem.201504576. Epub 2016 Mar 24.
A study on the influence of the cation coordination number, number of Lewis acid centers, concurrent existence of Lewis base sites, and structure topology on the catalytic activity of six new indium MOFs, has been carried out for multicomponent reactions (MCRs). The new indium polymeric frameworks, namely [In8 (OH)6 (popha)6 (H2 O)4 ]⋅3 H2 O (InPF-16), [In(popha)(2,2'-bipy)]⋅3 H2 O (InPF-17), [In3 (OH)3 (popha)2 (4,4'-bipy)]⋅4 H2 O (InPF-18), [In2 (popha)2 (4,4'-bipy)2 ]⋅3 H2 O (InPF-19), [In(OH)(Hpopha)]⋅0.5 (1,7-phen) (InPF-20), and [In(popha)(1,10-phen)]⋅4 H2 O (InPF-21) (InPF=indium polymeric framework, H3 popha=5-(4-carboxy-2-nitrophenoxy)isophthalic acid, phen=phenanthroline, bipy=bipyridine), have been hydrothermally obtained by using both conventional heating (CH) and microwave (MW) procedures. These indium frameworks show efficient Lewis acid behavior for the solvent-free cyanosilylation of carbonyl compounds, the one pot Passerini 3-component (P-3CR) and the Ugi 4-component (U-4CR) reactions. In addition, InPF-17 was found to be a highly reactive, recyclable, and environmentally benign catalyst, which allows the efficient synthesis of α-aminoacyl amides. The relationship between the Lewis base/acid active site and the catalytic performance is explained by the 2D seven-coordinated indium framework of the catalyst InPF-17. This study is an attempt to highlight the main structural and synthetic factors that have to be taken into account when planning a new, effective MOF-based heterogeneous catalyst for multicomponent reactions.
针对多组分反应（MCRs），开展了一项关于阳离子配位数、路易斯酸中心数量、路易斯碱位点的共存情况以及结构拓扑对六种新型铟金属有机框架（MOFs）催化活性影响的研究。通过常规加热（CH）和微波（MW）方法水热合成了新型铟聚合物框架，即[In8 (OH)6 (popha)6 (H2 O)4 ]⋅3 H2 O（InPF - 16）、[In(popha)(2,2'-联吡啶)]⋅3 H2 O（InPF - 17）、[In3 (OH)3 (popha)2 (4,4'-联吡啶)]⋅4 H2 O（InPF - 18）、[In2 (popha)2 (4,4'-联吡啶)2 ]⋅3 H2 O（InPF - 19）、[In(OH)(Hpopha)]⋅0.5 (1,7 - 菲咯啉)（InPF - 20）和[In(popha)(1,10 - 菲咯啉)]⋅4 H2 O（InPF - 21）（InPF = 铟聚合物框架，H3 popha = 5 - (4 - 羧基 - 2 - 硝基苯氧基)间苯二甲酸，phen = 菲咯啉，bipy = 联吡啶）。这些铟框架对羰基化合物的无溶剂氰基硅烷化反应、一锅法Passerini三组分（P - 3CR）反应和Ugi四组分（U - 4CR）反应表现出高效的路易斯酸行为。此外，发现InPF - 17是一种高活性、可回收且环境友好的催化剂，可用于高效合成α - 氨基酰基酰胺。催化剂InPF - 17的二维七配位铟框架解释了路易斯碱/酸活性位点与催化性能之间的关系。本研究旨在突出在设计用于多组分反应的新型、有效的基于MOF的非均相催化剂时必须考虑的主要结构和合成因素。
