The Use of Resorcinarene Cavitands in Metal‐Based Catalysis

Abstract

Catalytic chemistry involving coordination complexes based on resorcinarene cavitands has been little explored in comparison to the many studies concerning the use of such ligands in classical coordination chemistry or host–guest chemistry. The potential utility of resorcinarene cavitands in catalysis arises essentially from two features: (1) their ability to function as ligands suitable for metal confinement and thus to make reactions either shape selective or to enhance their rates through supramolecular assistance by the receptor subunit; (2) their ability to enforce steric interactions with a coordinated metal center and thereby favor carbon–carbon bond forming reactions. To date, limited use has been made of cavitands as platforms for the attachment of different ligating sites, in particular for the generation of multifunctional ligands giving rise to anchimeric assistance in catalytic reactions. This review is intended to show the promise that exists in this area. As generic cavitands can be easily expanded to result in large bowl‐shaped structures as well as capsular containers, it may be anticipated that future work in this field will focus on the synthesis of sophisticated, metallated microreactors (possibly made water‐soluble) for highly selective transformations, including polymerizations.

The 3rddegree of biomimetism: associating the cavity effect, ZnIIcoordination and internal base assistance for guest binding and activation

“… 16 , 17 The so-called bowl complexes, presenting three imidazole arms on their large rim, 18 were shown, when complexing a zinc cation, to present two labile sites in the cis position relative to each other, which opened new opportunities for recognition and reactivity. 19 – 23 …”

Académie des Sciences Prizes: M. Taillefer, G. Masson, L. Peng, D. Matt / Horst Dietrich Hardt Prize: L. H. Gade / Yamada–Koga Prize: J.‐E. Bäckvall

“…Matt's research currently focuses on metal confinement and molecular transition‐metal catalysts based on cavity‐shaped molecules, notably calixarenes, resorcinarenes, and cyclodextrins. He has reported in Chemistry—A European Journal on metal confinement through N‐heterocyclic carbenes, and in the European Journal of Organic Chemistry on resorcinarene cavitands in metal‐based catalysis …”

Mono‐ and Tri‐Functionalization of Trimethylresorcin[4]arenes

“…as multi-and mono-dentate bowlshaped ligands in several transition metal catalysed crosscoupling reactions. [6,7] Furthermore, tri-dentate resorcinarene ligands with imidazole binding sites were used as biomimetic model-compounds to study various zinc and copper based enzymatic binding sites, reported by Reinaud et al [8][9][10] Molecular resorcinarene-based capsules connected by three linkers have been reported, [11,12] some of them even with a photosensitive gate, [13] as well as dimers with only one covalent bond between the resorcinarene-units. [14,15] All these examples derive from tri-or mono-functionalized resorcinarenes.…”