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Hydrogen-bonding organocatalysis has emerged as a promising biomimetic alternative to Lewis acid catalysis. Urea, thiourea and squaramide moieties represent the most common hydrogen-bond donors used for the preparation of these catalysts. However, their significant tendency to undergo self-quenching (self-aggregation) often decreases their solubility and reactivity. Recently, scientists have found a promising way around this problem by immobilizing the hydrogen-bonding organocatalysts on metal-organic frameworks (MOFs). Along with advantageous modular synthesis and recycling properties, the tunable porosity and topology of MOFs also allows fast mass transport and/or interactions with substrates. Herein, we highlight the existing examples dealing with the fabrication and testing of hydrogen-bonding organocatalyst-containing MOFs, providing also our vision for further advances in this area. The results derived from these studies will likely serve as inspiration for the future development of superior hydrogen-bonding organocatalysts to accomplish in confined spaces chemical transformations that are either slow or unaffordable under standard homogeneous conditions.Universität Regensburg, Deutsche Forschungsgemeinschaft (DFG, 9209720), Universidad de Zaragoza (JIUZ-2014-CIE-07), Consejo Superior de Investigaciones Científicas (CSIC, PIE-201580I010) and Diputación General de Aragón (DGA) Research Group E-104) are acknowledged for financial support. J. V. A.-R. thanks DGA for a predoctoral fellowship. D. D. D. thanks DFG for the Heisenberg Professorship Award.Peer Reviewe

Metal–organic frameworks (MOFs) bring new life to hydrogen-bonding organocatalysts in confined spaces