Metal Organic Frameworks as Solid Catalysts in Condensation Reactions of Carbonyl Groups

Abstract

This review summarizes the use of metal organic frameworks (MOFs) as solid catalysts for condensation reactions. After an introductory section, in which condensation reactions are generally presented, a list of the MOFs employed as condensation catalyst is given. The main part of the present review is organized according to the use of MOFs as solid acids, solid bases or as bi-functional solids containing both acid and basic sites. Throughout the review, the emphasis has been made on discussing the stability of the MOFs, their reusability and in providing a comparison of the performance of MOFs with respect to other homogeneous and heterogeneous catalysts. Finally, we summarize the current state-of-the-art and provide our view on future trends and developments in this field.

A new cyclic binuclear Ni(II) complex as a catalyst towards nitroaldol (Henry) reaction

“…Depending on the nature of the reactants, the reaction involves the formation of one or two asymmetric centres at the new carbon-carbon junction, where the optically active forms are useful intermediates in the synthesis of biologically active compounds [4] or polyfunctionalized materials [10]. The stereoselectivity of the reaction was first time reported by Shibasaki in 1992 [11] and a number of works have appeared in recent years [3][4][5][6], showing the current interest of the Henry reaction and its application. The reaction has been studied in homogeneous [3][4][5][6], heterogeneous [12][13][14], ionic liquids or supercritical fluids [15], mesoporous nanocomposite conditions [16], etc.…”

“…The reaction can be catalyzed by inorganic/organic bases or metal complexes [2][3][4][5][6][7][8][9] and can be used as a tool for the syntheses of a variety of valuable building blocks of pharmaceutical significance [3][4][5][6]. Depending on the nature of the reactants, the reaction involves the formation of one or two asymmetric centres at the new carbon-carbon junction, where the optically active forms are useful intermediates in the synthesis of biologically active compounds [4] or polyfunctionalized materials [10].…”

Acid‐Activated Carbon Materials: Cheaper Alternative Catalysts for the Synthesis of Substituted Quinolines

“…[24] Nevertheless, we have recently reported on the first examples of Friedländer reaction promoted by a metal-organic framework, [Cu 3 (BTC) 2 ], a mesoporous material exhibiting the highest activity mainly because of the higher number of catalytic sites located on metallic centers. [25][26][27] Friedländer condensation is considered as an atom-economic reaction that proceeds through double condensation between 2-aminoaryl carbonyl compounds with other carbonyl components having active methylenic units at a-position affording quinolines. [28,29] These nitrogen heterocycles represent an important class of compounds as part of many natural products and building blocks useful for the preparation of synthetic compounds with application in medicine, food, catalysis, dye, materials, refineries, and electronics.…”

Design and Synthesis of an Au@MIL‐53(NH2) Catalyst for a One‐Pot Aerobic Oxidation/Knoevenagel Condensation Reaction

“…This one-pot reaction sequence can be viewed as two separate steps: a gold-promoted aerobic alcohol oxidation [44] followed by an aminepromoted Knoevenagel reaction to furnish 2-benzylidenemalononitrile (3). [64,65] The control reaction in the absence of catalyst gave no conversion of the benzyl alcohol (1) starting material ( Table 2, entry 1). Over 99 % yield of desired product 3 was obtained by using 1 mol-% of Au@MIL-53(NH 2 ) as the bifunctional catalyst, and this demonstrates the powerful multistep transformation activity of our Au@MIL-53(NH 2 ) catalyst (Table 2, entry 2).…”