We report the synthesis of two [N,N]-donor ligands (5 a-b) containing a 2-chalcogenazoline as the structural motif. These compounds were synthesized from a common intermediate Fischer type aminocarbene complex (3). The palladium-complexes of these [N,N]-donor ligands were successfully used as catalytic precursors in the Mizoroki-Heck coupling reaction between aryl halides and methyl acrylate, styrene and ethylene. For methyl acrylates, high yields with TOF values between 0.6 and 5.5 × 10 5 h À 1 were obtained. In the case of ethylene, we reached high regioselectivities to obtain a diversity of styrene derivatives under soft pressure conditions, with good values of TON and TOF.

P-pyrrole phosphines (R 2 Ppyr), in which a pyrrole group is directly bonded to the phosphorus atom, act as monodentate k-P ligands towards gold(I) center to afford either neutral or cationic mononuclear complexes as well as neutral dinuclear complexes. All of these new gold(I) complexes have been structurally characterized and their first uses in catalysis have demonstrated their effectiveness as precatalysts for the enyne cycloisomerization reactions.

The Suzuki-Miyaura cross-coupling is one of the most useful synthetic tools to build CÀ C bonds, but the use of hydroxyaryl halides to direct access hydroxy-byaryls still remains a challenge. For the carbonylative version of the reaction, the synthesis of hydroxybiaryl ketones is commonly solved by protecting group strategies. In this work, we report a protocol of carbonylative Suzuki-Miyaura coupling catalysed by a [N,P]-PdCl 2 complex using aryl halides, various aryl boronic acids and CO. We were able at first to obtain biphenyls, finding a singular reactivity towards 2-bromophenol, that later was extended to the carbonylation reaction, resulting in methodology that allows the obtention of 2-hydroxybiaryl ketones, with a functional group tolerance toward amines, alkoxy, ketones, esters, and halides.