Synthesis of Thiapillar[6]arenes Bearing Redox-Active (Hydro)quinone Groups. Electrochemical and XRD Study.

Pillar[]arenes are among the newest members of the macrocyclic family. Nevertheless, their conformational behavior and binding properties as well as redox properties of dealkylated pillar[]arenes are well-studied. At the same time, introducing a heteroatom into a cyclophane macrocycle is already known to alter all the above properties drastically.

Enantiodiscrimination of Inherently Chiral Thiacalixarenes by Residual Dipolar Couplings.

Inherently chiral compounds, such as calixarenes, are chiral due to a nonplanar three-dimensional (3D) structure. Determining their conformation is essential to understand their properties, with nuclear magnetic resonance (NMR) spectroscopy being one applicable method. Using alignment media to measure residual dipolar couplings (RDCs) to obtain structural information is advantageous when classical NMR parameters like the nuclear Overhauser effect (NOE) or -couplings fail.

Synthesis of inherently chiral calixarenes via direct mercuration of the partial cone conformation.

Direct mercuration of calix[4]arene immobilized in the partial cone conformation led to the meta-substituted isomer which was subsequently subjected to Pd-catalysed coupling (C-H activation) with the neighbouring aromatic subunit. Regioselective mercuration thus enabled access to a novel type of inherently chiral calixarenes with a highly distorted cavity potentially applicable to the design of new chiral receptors.