Anion-Based Self-assembly of Resorcin[4]arenes and Pyrogallol[4]arenes.

Spatial sequestration of molecules is a prerequisite for the complexity of biological systems, enabling the occurrence of numerous, often non-compatible chemical reactions and processes in one cell at the same time. Inspired by this compartmentalization concept, chemists design and synthesize artificial nanocontainers (capsules and cages) and use them to mimic the biological complexity and for new applications in recognition, separation, and catalysis. Here, we report the formation of large closed-shell species by interactions of well-known polyphenolic macrocycles with anions. It has been known since many years that C-alkyl resorcin[4]arenes (R4C) and C-alkyl pyrogallol[4]arenes (P4C) narcissistically self-assemble in nonpolar solvents to form hydrogen-bonded capsules. Here, we show a new interaction model that additionally involves anions as interacting partners and leads to even larger capsular species. Diffusion-ordered spectroscopy and titration experiments indicate that the anion-sealed species have a diameter of >26 Å and suggest stoichiometry (M)6(X-)24 and tight ion pairing with cations. This self-assembly is effective in a nonpolar environment (THF and benzene but not in chloroform), however, requires initiation by mechanochemistry (dry milling) in the case of non-compatible solubility. Notably, it is common among various polyphenolic macrocycles (M) having diverse geometries and various conformational lability.

Dodecameric Anion-Sealed Capsules based on Pyrogallol[5]arenes and Resorcin[5]arenes.

The paper reports formation of exceptionally large capsular species (diameter of c. a. 30 Å) by interactions of polyphenolic macrocycles with 5-fold symmetry with anions. Pyrogallol[5]arenes and resorcin[5]arenes interact with anions via hydrogen bonds involving phenolic OH groups or aromatic CH groups. Based on NMR titration experiments, diffusion coefficients, and geometric requirements, it is postulated that the capsules have (P5H)12 (X- )60 or (R5H)12 (X- )60 stoichiometry and a unique geometry of one of the Platonic solids-a dodecahedron. The capsules exist in THF and in benzene, but not in chloroform, reflecting competitive effects in the solvation of anions. It is also demonstrated that mechanochemical pre-treatment (dry-milling) of solid samples is indispensable to initialize self-assembly in benzene.

Higher Analogues of Resorcinarenes and Pyrogallolarenes: Bricks for Supramolecular Chemistry.

Easy scalable and eco-friendly syntheses of resorcin[5]arene, pyrogallol[5]arene, (2-nitro)resorcin[5]arene, (2-carboxyl)resorcin[5]arene, and resorcin[7]arene are presented and a wide range of upper-rim modifications is demonstrated. The macrocycles open the door toward expanding the rich covalent and supramolecular chemistry of [4]arenes with analogues having unique 5-fold and 7-fold symmetry.

The Synthesis of 5-Amino-dihydrobenzo[b]oxepines and 5-Amino-dihydrobenzo[b]azepines via Ichikawa Rearrangement and Ring-Closing Metathesis.

The combination of Ichikawa's rearrangement and a ring-closing metathesis reaction of allyl carbamates is presented as a method for the preparation of 5-amino-substituted 2,5-dihydro-benzo[b]oxepines, 2,5-dihydro-benzo[b]azepines, and 2,5-dihydro-benzo[b]thiepins. It was demonstrated that the use of nonracemic allyl carbamates enables the synthesis of enantioenriched benzo-fused seven-membered heterocycles. Finally, it was shown that further functionalization of the obtained structures allows access to pharmacologically active 5-amino-substituted 2,3,4,5-tetrahydro-1-benzo[b]oxepine scaffolds.