Direct arylation of 5-octylthieno[3,4-c]pyrrole-4,6-dione with a series of functionalized aryl iodides via C-H bond activation is demonstrated in a deep eutectic solvent made of choline chloride and urea in non-anhydrous conditions and without exclusion of air. This is the first demonstration of a thiophene-aryl coupling via direct arylation in deep eutectic solvents.

Oxetane nudges in the DoM direction! Regioselective ortho-lithiation induced by an oxetane ring has been achieved. The reaction provides easy access to ortho-functionalized 2-aryloxetanes also through a lithiation/borylation Suzuki–Miyaura cross-coupling. The lithiation-directing ability of oxetane and the proton transfer mechanism have been investigated by competitive metalation and kinetic isotope effect studies

A valuable and direct method to access 2-substituted-2-phenyloxetanes by electrophilic quenching of the corresponding 2-lithiated derivative has, for the first time, been described. 2-Lithiated-2-phenyloxetane was found to be configurationally unstable. Evidence is presented to show that electron-transfer processes are also operative in the coupling reactions with electrophiles.

The first structure of an aromatic bis(trifluoroborate) dipotassium salt, elucidated by the combination of crystallography, DFT calculations, topological and non-covalent interaction analysis, discloses a 3D network undergoing spontaneous self-assembly thanks to the massive participation of weak intra- and intermolecular interactions for which fluorine atoms proved to play a leading role.

Die erste regioselektive ortho‐Lithiierung, die durch einen Oxetanring induziert wird, wurde entwickelt. Die Reaktion bietet leichten Zugang zu ortho‐funktionalisierten 2‐Aryloxetanen auch durch Lithiierung/Borylierung und Suzuki‐Miyaura‐Kreuzkupplung. Die dirigierende Wirkung des Oxetans und der Protonentransfermechanismus wurden anhand konkurrierender Metallierungen und kinetischer Isotopeneffekte untersucht.