The design of artificial catalysts able to compete with the catalytic proficiency of enzymes is an intense subject of research. Non-covalent interactions are thought to be involved in several properties of enzymatic catalysis, notably (i) the confinement of the substrates and the active site within a catalytic pocket, (ii) the creation of a hydrophobic pocket in water, (iii) self-replication properties and (iv) allosteric properties. The origins of the enhanced rates and high catalytic selectivities associated with these properties are still a matter of debate. Stabilisation of the transition state and favourable conformations of the active site and the product(s) are probably part of the answer. We present here artificial catalysts and biomacromolecule hybrid catalysts which constitute good models towards the development of truly competitive artificial enzymes.

Supramolecular catalysis is a rapidly expanding discipline which has benefited from the development of both homogeneous catalysis and supramolecular chemistry. The properties of classical metal and organic catalysts can now be carefully tailored by means of several suitable approaches and the choice of reversible interactions such as hydrogen bond, metal-ligand, electrostatic and hydrophobic interactions. The first part of these two subsequent reviews will be dedicated to catalytic systems for which non-covalent interactions between the partners of the reaction have been designed although mimicking enzyme properties has not been intended. Ligand, metal, organocatalyst, substrate, additive, and metal counterion are reaction partners that can be held together by non-covalent interactions. The resulting catalysts possess unique properties compared to analogues lacking the assembling properties. Depending on the nature of the reaction partners involved in the interactions, distinct applications have been accomplished, mainly (i) the building of bidentate ligand libraries (intra ligand-ligand), (ii) the building of di- or oligonuclear complexes (inter ligand-ligand), (iii) the alteration of the coordination spheres of a metal catalyst (ligand-ligand additive), and (iv) the control of the substrate reactivity (catalyst-substrate). More complex systems that involve the cooperative action of three reaction partners have also been disclosed. In this review, special attention will be given to supramolecular catalysts for which the observed catalytic activity and/or selectivity have been imputed to non-covalent interaction between the reaction partners. Additional features of these catalysts are the easy modulation of the catalytic performance by modifying one of their building blocks and the development of new catalytic pathways/reactions not achievable with classical covalent catalysts.

During the last few decades, rhodium-catalysed asymmetric hydrogenation of diverse alkene classes has emerged as a powerful synthetic tool in the pharmaceutical industry, contributing to the manufacturing of chiral drugs, recent drug candidates for clinical trials, and major synthetic precursors of drugs. Numerous efficient chiral rhodium complexes, most of which are derived from enantiopure phosphorus ligands, have been employed for the preparation of chiral drugs and intermediates thereof. This review article is intended to provide an updated overview of the most striking contributions in this field, organised according to substrate class: acrylate derivatives, itaconate derivatives, α-substituted enamides, α-arylenol acetates, and minimally functionalised olefins.