New horizons for catalysis disclosed by supramolecular chemistry

Abstract

Recent advancements in supramolecular catalysis are reviewed, which show the potential of related tools when applied to organic synthesis. Such tools are recognized as innovative instruments that can pave the way to alternative synthetic strategies.

Diametric calix[6]arene-based phosphine gold(I) cavitands

“…One of the latest challenges in supramolecular chemistry is the design and development of novel macrocyclic-based entities able to influence the catalytic activities of the metal center [1][2][3]. In this context, phosphines represent the most exploited class of ligands in homogeneous catalysis [4].…”

Organic radical reactions confined to containers in supramolecular systems

“…Chemists are learning to simulate such behavior to tackle general problems posed by reactive species in catalysis. 7 The earliest systems involved the covalent carcerands that contained and “tamed” reactive species – famously, cyclobutadiene. 8 To access larger spaces for confinement, chemists designed and synthesized supramolecular hosts to encapsulate and isolate guest molecules.…”

Resorcin[4]arene Hexameric Capsule as a Supramolecular Catalyst in Elimination and Isomerization Reactions

“…Once bound, substrate activation is carried out by specific amino acid side chains that adorn the inner surface of the cavity by means of a combination of covalent and/or weak intermolecular interactions leading to the stabilization of intermediate species and transition states of the reaction with impressive accelerations, substrate, and product selectivities. The development of artificial catalytic systems able to activate substrates and to stabilize intermediate species through weak non-covalent interactions is the scope of supramolecular catalysis [1,2]. Several examples of supramolecular catalysts [3,4,5] have been introduced in the recent years [6] where the catalytic host is designed to bind substrates, accelerate reactions, and steer product [7,8] and substrate [9] selectivities thanks to confinement effects [10,11,12].…”