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• 112-54-9 Dodecanal 
• 108-46-3 recorcinol 

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• 1328884-38-3 C₁₆₀H₂₀₈O₁₆ 
• 1328884-39-4 C₁₂₈H₁₃₆Cl₈O₁₆ 
• 1328884-37-2 C₁₂₈H₁₄₄O₁₆ 
• 1328884-21-4 C₁₀₀H₁₃₆O₈ 
• 1328884-20-3 C₁₀₀H₁₃₆O₈ 
• 242129-43-7 C₉₀H₁₁₂O₂₀N₆ 

Relevant academic research and scientific papers

Concentration-Dependent Self-Assembly of an Unusually Large Hexameric Hydrogen-Bonded Molecular Cage

The sizes of available self-assembled hydrogen-bond-based supramolecular capsules and cages are rather limited. The largest systems have volumes of approximately 1400–2300 ?3. Herein, we report a large, hexameric cage based on intermolecular am

Requirements for Terpene Cyclizations inside the Supramolecular Resorcinarene Capsule: Bound Water and Its Protonation Determine the Catalytic Activity

The elucidation of the requirements for efficient catalysis within supramolecular host systems is an important prerequisite for developing novel supramolecular catalysts. The resorcinarene hexamer has recently been shown to be the first supramolecular catalyst to promote the tail-to-head terpene cyclization in a biomimetic fashion. We herein present the synthesis of a number of resorcinarene-based macrocycles composed of different ratios of resorcinol and pyrogallol units capable of self-assembly and compare the corresponding assemblies regarding their catalytic activity in the cyclization of monoterpenes. The assemblies were investigated in detail with respect to a number of properties including the encapsulation of substrate and ion pairs, the structural incorporation of water, and the response to externally added acid (HCl). The results obtained strongly indicate that water incorporated into the hydrogen-bond network of the self-assembled structure plays an integral role for catalysis, effectively acting as a proton shuttle to activate the encapsulated substrate. These findings are also supported by molecular dynamics simulations, providing further insight into the protonation pathway and the relative energies of the intermediates involved.

Supramolecular Capsules: Strong versus Weak Chalcogen Bonding

Resorcin[4]arene cavitands containing either 2,1,3-benzotelluradiazole or 2,1,3-benzothiadiazole motifs were dimerized to supramolecular capsules by chalcogen bonding. Their respective behavior varied depending on the interaction strength of the chalcogen bonds with Te forming strong interactions and S weak interactions. The tremendous strength of multiple 2Te–2N square interactions led to formation of a chalcogen-bonded dimeric capsule in all solvents, as shown by X-ray crystal structures with 16 short Te???N distances (≤2.9 ?) and confirmed by native electrospray ionization mass spectrometry (ESI-MS). With the S cavitand, solvent-dependent crystallization resulted in different arrangements: either a shifted 2S–2N square-bonded capsule or an interlocked 1D polymer with an infinite π–π stacking array. The association constant to form the dimeric capsule in [D8]THF at 283 K, solely based on weak 2S–2N square interactions, was determined as Ka=786 m?1.

Br?nsted Acid-Catalyzed Carbonyl-Olefin Metathesis inside a Self-Assembled Supramolecular Host

Carbonyl–olefin metathesis represents a powerful yet underdeveloped method for the formation of carbon–carbon bonds. So far, no Br?nsted acid based method for the catalytic carbonyl–olefin metathesis has been described. Herein, a cocatalytic system based on a simple Br?nsted acid (HCl) and a self-assembled supramolecular host is presented. The developed system compares well with the current benchmark catalyst for carbonyl–olefin metathesis in terms of substrate scope and yield of isolated product. Control experiments provide strong evidence that the reaction proceeds inside the cavity of the supramolecular host. A mechanistic probe indicates that a stepwise reaction mechanism is likely.

Iminium Catalysis inside a Self-Assembled Supramolecular Capsule: Scope and Mechanistic Studies

Although iminium catalysis has become an important tool in organic chemistry, its combination with supramolecular host systems has remained largely unexplored. We report the detailed investigations into the first example of iminium catalysis inside a supramolecular host. In the case of 1,4-reductions of α,β-unsaturated aldehydes, catalytic amounts of host are able to increase the enantiomeric excess of the products formed. Several control experiments were performed and provided strong evidence that the modulation of enantiomeric excess of the reaction product indeed stems from a reaction on the inside of the capsule. The origin of the increased enantioselectivity in the capsule was investigated. Furthermore, the substrate and nucleophile scope were studied. Kinetic investigations as well as the kinetic isotope effect measured confirmed that the hydride delivery to the substrate is the rate-determining step inside the capsule. The exploration of benzothiazolidines as alternative hydride sources revealed an unexpected substitution effect of the hydride source itself. The results presented confirm that the noncovalent combination of supramolecular hosts with iminium catalysis is opening up new exciting possibilities to increase enantioselectivity in challenging reactions.

Host-Catalyzed Cyclodehydration–Rearrangement Cascade Reaction of Unsaturated Tertiary Alcohols

The Br?nsted acidic resorcin[4]arene hexamer can be applied as an effective catalyst in the dehydrative cyclization and subsequent rearrangement of unsaturated tertiary alcohols. This is the first report on catalyzing such a reaction with a Br?nsted acid. Scope and limitations of this cyclopentene-forming reaction sequence are presented. Furthermore, substrate-selective conversion as well as competitive inhibition are described and provide evidence that the reactions proceed within the cavity of the self-assembled structure. Additionally, a cyclobutanone-forming intramolecular hydride transfer of an encapsulated cyclopropyl acetate is reported. (Figure presented.).

Polystyrene-supported bifunctional resorcinarenes as cheap, metal-free and recyclable catalysts for epoxide/CO2 coupling reactions

We here report the synthesis of bifunctional catalysts that can be assembled using simple, cheap and accessible building blocks based on resorcinarenes, and their application as efficient, one-component homogeneous catalysts in the coupling of both terminal and internal epoxides with carbon dioxide affording their cyclic carbonate products. Furthermore, a heterogeneous version was also prepared that combines the activity of these bifunctional systems with excellent stability and recycling potential, allowing for a turnover of >1250. This newly prepared organocatalyst obviates the use of any metal, solvent or additives marking it as an attractive catalyst for CO2 valorization.

Iminium Catalysis inside a Self-Assembled Supramolecular Capsule: Modulation of Enantiomeric Excess

The noncovalent combination of a supramolecular host with iminium organocatalysis is described. Due to cation–π interactions the reactive iminium species is held inside the host and reacts in this confined environment. The products formed differ up to 92 % ee from the control experiments without added host. A model rationalizing the observed difference is presented.

Intramolecular hydroalkoxylation catalyzed inside a self-assembled cavity of an enzyme-like host structure

Self-assembled resorcin[4]arene hexamer catalyzes the intramolecular hydroalkoxylation of unsaturated alcohols to the corresponding cyclic ethers under mild conditions. The mode of catalysis and encapsulation-based substrate selectivity of the host efficiently mimic the basic principle of operation observed in enzymes.

Calixarene-mediated liquid-membrane transport of choline conjugates

A series of supramolecular calixarenes efficiently transport distinct molecular species through a liquid membrane when attached to a receptor-complementary choline handle. Calix[6]arene hexacarboxylic acid was highly effective at transporting different target molecules against a pH gradient. Both carboxylic-and phosphonic-acid-functionalized calix[4]arenes effect transport without requiring a pH or ion gradient. NMR binding studies, two-phase solvent extraction, and three-phase transport experiments reveal the necessary and subtle parameters to effect the transport of molecules attached to a choline "handle". On the other hand, rescorin[4]arene cavitands, which have similar guest recognition profiles, did not transport guest molecules. These developments reveal new approaches towards attempting synthetic-receptor-mediated selective small-molecule transport in vesicular and cellular systems.