Trisulfonamide calix[6]arene-catalysed Michael addition to nitroalkenes

We describe the application of a novel family of trisulfonamide (TSA) calix[6]arenes in general acid catalysis. Hydrogen-bonding interactions between acidic TSA and methanol boosted the reactivity of the Michael addition of indoles to nitroalkene derivatives. The transformation occurs at a low catalyst loading of 5 mol%, allowing for the synthesis of nitroalkanes with good yields and functional group tolerance

Electrochemically Triggered Co-Conformational Switching in a [2]catenane Comprising a Non-Symmetric Calix[6]arene Wheel and a Two-Station Oriented Macrocycle

Catenanes with desymmetrized ring components can undergo co-conformational rearrangements upon external stimulation and can form the basis for the development of molecular rotary motors. We describe the design, synthesis and properties of a [2]catenane consisting of a macrocycle—the ‘track’ ring—endowed with two distinct recognition sites (a bipyridinium and an ammonium) for a calix[6]arene—the ‘shuttle’ ring. By exploiting the ability of the calixarene to thread appropriate non-symmetric axles with directional selectivity, we assembled an oriented pseudorotaxane and converted it into the corresponding oriented catenane by intramolecular ring closing metathesis. Cyclic voltammetric experiments indicate that the calixarene wheel initially surrounds the bipyridinium site, moves away from it when it is reduced, and returns in the original position upon reoxidation. A comparison with appropriate model compounds shows that the presence of the ammonium station is necessary for the calixarene to leave the reduced bipyridinium site

Covalent capture of oriented calix[6]arene rotaxanes by a metal-free active template approach

We describe the active template effect of a calix[6]arene host towards the alkylation of a complexed pyridylpyridinium guest. The acceleration of the reaction within the cavity is significant and rim-selective, enabling the efficient preparation of rotaxanes with full control of the mutual orientation of their nonsymmetric components

Plugging a bipyridinium axle into multichromophoric calix[6]arene wheels bearing naphthyl units at different rims

Tris-(N-phenylureido)-calix[6]arene derivatives are heteroditopic non-symmetric molecular hosts that can form pseudorotaxane complexes with 4,4'-bipyridinium-type guests. Owing to the unique structural features and recognition properties of the calix[6]arene wheel, these systems are of interest for the design and synthesis of novel molecular devices and machines. We envisaged that the incorporation of photoactive units in the calixarene skeleton could lead to the development of systems whose working modes can be governed and monitored by means of light-activated processes. Here we report on the synthesis, structural characterization, and spectroscopic, photophysical and electrochemical investigation of two calix[6]arene wheels decorated with three naphthyl groups anchored to either the upper or lower rim of the phenylureido calixarene platform. We found that the naphthyl units interact mutually and with the calixarene skeleton in a different fashion in the two compounds, which thus exhibit a markedly distinct photophysical behavior. For both hosts, the inclusion of a 4,4'-bipyridinium guest activates energy- and/or electron-transfer processes that lead to non-trivial luminescence changes

Calixarenes and Nanoparticles

The anchoring of functional organic coatings on the surface of inorganic nanoparticles has been and still is the topic of intense research activity for the development of novel nanomaterials. Within this context metal nanoparticles decorated with synthetic receptors have been quite extensively employed to further expand the scope of supramolecular chemistry. In this chapter we offer a general survey on the use of calixarene derivatives as functional components for the preparation of gold and silver nanoparticles. A particular emphasis is placed on the exploitation of the chemical and structural information stored in properly functionalized calixarene macrocycles as control element during the synthesis to define the nanoparticles nuclearity and the recognition capability of the macrocycle for the manufacturing of nanodevices with potential applications in sensing and biomedicine

Recognition of Amides By New Rigid Calix[4]arene-based Cavitands

The synthesis of new hosts specifically designed for the recognition of amides, characterized by two binding regions:  a rigid calix[4]arene cavity and a sidearm, inserted at its rim, able to form strong hydrogen bonds, is described. The binding abilities of the new receptors toward amides of general structure R1CONR2R3 have been investigated in CDCl3 solution by 1H NMR spectroscopy. When the additional binding site is the N-phenylureido group spaced by a methylene unit from the apolar cavity, binding constants up to 756 M-1 were measured. Neither the two separate potential binding sites, nor the model host, where the calix[4]arene skeleton is flexible show detectable binding ability toward the series of guests examined. The rigidity of the calix[4]arene apolar cavity is the key control element in determining the efficiency of these molecular recognition processes. The presence of NH groups in the guest controls the efficiency and selectivity of binding

From carbohydrates to the discovery of prounced heteroatomic effects on anionically accelerated [3,3]-sigmatropic rearrangements

[[abstract]]The (Z)-(iodovinyl)oxetane 12 was prepared from D-glucose and the acyclic analog 18 was obtained from D-mannitol. Following the generation of their lithium derivatives by halogen−metal exchange, coupling to the enantiopure vinyl-substituted norbornanones 20, 23, and 29 proceeded exclusively via endo attack to deliver the targeted exo-carbinols. The anionic oxy-Cope rearrangements of 21 and 24 were seen to differ appreciably in rate. While the sulfur derivative 24 experiences [3,3] sigmatropy with a half-life of less than a minute at −78 °C, its oxygen analogue 21 proved unreactive below −20 °C under entirely comparable conditions. This phenomenon is critically examined in a synthetic context involving 26 and 30, where the heavily functionalized acyclic side chain involved previously is supplanted by an oxetane assembly. In the sulfur example, isomerization occurs very rapidly as before with 100% transfer of chirality. The kinetic response of vinyl ether 26 now proved to be entirely comparable. However, the pathway followed in this instance was intramolecular nucleophilic attack by the “naked” alkoxide at the less substituted C−O bond of the oxetane with ring cleavage and formation of alcohol 28. The global findings provide a glimpse of the subtle way in which [3,3]-sigmatropic transpositions can be modulated by heteroatomic substitution.[[notice]]補正完