Synthesis of 4-hydroxypiperidines containing a quaternary stereocenter by aza-Prins cyclization.

A straightforward and highly diastereoselective synthesis of -4-hydroxypiperidines is presented. This method allows access to C2 and C4 substituted piperidines, bearing a tetrasubstituted carbon stereocenter at C4. -Disubstituted homoallylic amines and ketoaldehydes as carbonyl partners have been rarely used in aza-Prins cyclizations, expanding the scope of this reaction.

Of perfluorinated aryllead(II) complexes.

The pentafluorophenyl moiety CF was succesfully employed for the first time in lead(II) chemistry. We are reporting on the stable and soluble organolead(II) polymer [Pb(CF)(dx)] (dx = dioxane). An example of a Pb(II) "ate" complex paired with a trimetallic magnesium cation is also presented.

Electrostatic electronic interactions within oxidized multinuclear Pt(bipyridine)(dithiolene) complexes.

Bi- and trimetallic platinum(bipyridine)(dithiolene) complexes involving different organic linkers between the redox active platinum(dithiolene) moieties have been synthesized and studied by electrochemistry and spectroelectrochemistry. Cyclic voltammetry experiments carried out on these multinuclear complexes in dichloromethane using [NBu][PF] as the supporting salt show only one oxidation process involving the metallacycles. Nevertheless, spectro-electrochemical studies, carried out under the same conditions, show a different evolution of the spectra during oxidation depending on the position of the metallacycles on the phenyl ring.

Repurposing a supramolecular iridium catalyst secondary Zn⋯O[double bond, length as m-dash]C weak interactions between the ligand and substrate leads to -selective C(sp)-H borylation of benzamides with unusual kinetics.

The iridium-catalyzed C-H borylation of benzamides typically leads to and selectivities using state-of-the-art iridium-based ,-chelating bipyridine ligands. However, reaching selectivity patterns requires extensive trial-and-error screening molecular design at the ligand first coordination sphere. Herein, we demonstrate that triazolylpyridines are excellent ligands for the selective iridium-catalyzed C-H borylation of tertiary benzamides and, importantly, we demonstrate the almost negligible effect of the first coordination sphere in the selectivity, which is so far unprecedented in iridium C-H bond borylations.

Mixed-ligand, radical, gold bis(dithiolene) complexes: from single-component conductors to controllable NIR-II absorbers.

Neutral radical bis(dithiolene) gold complexes [Au(dt)]˙ are known to exhibit a strong absorption in the 1400-2000 nm NIR absorption range. Here, we demonstrate that the NIR signature of mixed-ligand bis(dithiolene) gold complexes [Au(dt)(dt)]˙ associating two different dithiolene, dt and dt, is found at higher energy, out of the range of the homoleptic analogs [Au(dt)]˙ and [Au(dt)]˙, in the looked-after NIR-II 1000-1400 nm absorption range. An efficient synthetic approach towards precursor mixed-ligand monoanionic gold bis(dithiolene) complexes [Au(dt)(dt)] is reported.