Abstract A highly diastereoselective synthesis of cationic permethylated α- and β-cyclodextrins (α-CDs and β-CDs), incorporating a quaternary ammonium unit bridging two adjacent glucose units, has been developed. This novel methodology provides access to amphipathic α-CDs equipped with an…
Abstract Cyclodextrins (CDs) are bio-based and biodegradable oligosaccharides, enzymatically derived from starch, offering low toxicity and renewability, thus representing an interesting renewable feedstock. While chemical modification allows for precise tailoring of their properties, greater…
Abstract Molecular structures comprising naturally-occurring, stereodefined cyclodextrins and binaphthyls as bridging units have been realized, designed in such a way that the stereocommunication mode between the two chiral entities is unfavourable ('chiral mismatch'). The induced strain translates…
Abstract Four cis-chelating diphosphanes derived from cyclodextrins (CDs), each featuring a distinct intracavity environment, compel NiII or PdII metal centers to reside within α- or β-CD cavities. Nickel(II) complexes of these metal-confining ligands act as active catalysts in ethylene…
Abstract In this study, water-soluble colloidal platinum nanoparticles (Pt NPs) have been stabilized with novel thiolated cyclodextrins (CD-SH) and their catalytic performance has been investigated. We varied the size of the CD cycle (α-CD/β-CD), the degree of thiolation (one or two thiol groups…
Abstract When aiming at the direct use of CO2 for the preparation of advanced/value-added materials, the synthesis of CO2/olefin copolymers is very appealing but challenging. The δ-lactone 3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one (EVP), synthesized by telomerization of CO2 with 1,3-butadiene,…
Summary Rigid terdentate ‘pincer' ligands containing a bridgehead N-heterocyclic carbene (NHC) donor attract considerable interest as spectators in transition metal complexes with broad scope and potential applications in the fields of catalysis, medicinal chemistry and material science. This…
Summary Pyridine Ring-Expanded dicarbene Pincer ligands were synthesized and some representative complexes with Ni and Cr show distinct geometrical and electronic characteristics from analogues with 5-membered ring heterocycles, opening new possibilities for pincer ligands featuring carbene…
Graphical Abstract Two for the price of one! Depending on the experimental conditions, two dramatically different diphosphanes can be obtained from diphenyl(2-phosphanylphenyl)phosphane and an α-cyclodextrin-derived dimesylate. The metal confining properties of the cavity-shaped ligands have been…
Abstract Chiroptical materials are gaining increasing interest due to their innovative character and their applications in optoelectronics and data encryption technologies. Fully harnessing the potential of building blocks from the “chiral pool”, such as native cyclodextrins (CDs), as they often…
Abstract Carbonylmetallates [m]−, such as [MoCp(CO)3]−, [Mn(CO)5]−, [Co(CO)4]−, have long been successfully used in the preparation of hundreds of metal-metal bonded carbonyl complexes and clusters, in particular of the heterometallic type. We focus here on situations where [m]− can be viewed as a…
Abstract A ß-cyclodextrin-based diphosphane with metal confining properties was efficiently synthesized thanks to an unprecedented Smiles-like rearrangement of 1-diphenylphosphino-2-phosphinobenzene in the presence of excess n-BuLi. The cis-chelating bidentate ligand is capable of forming very…
Abstract The presence of a permethylated α-cyclodextrin (α-CD) cavity in a chelating P,N ligand promotes exclusive formation of 1 : 1 ligand/metal complexes. In MX2 complexes, one of the two halido ligands is forced to reside inside the CD hollow while the second one is pointing outside. Unlike its…
Abstract Cavity-shaped ligands offer unique opportunities for influencing the first sphere of coordination of metals because of their capacity to act as containers for metal centers and/or preorganization platforms. These unique properties are of particular importance in asymmetric metal catalysis…
Abstract Gold(I) complexes containing monodentate PIII ligands built upon methylated α-cyclodextrins have been synthesized and assessed in the cycloisomerization of 1,6-enynes, two of the reactions studied involving prochiral substrates. Their performance was compared with that of previously…
