Aza-Heck cyclizations are an emerging method for the construction of chiral N-heterocyclic systems. In these processes, an activated N-O bond replaces the C-X bond (X = halide, OTf) used in conventional Heck reactions, with the associated aza-Pd(ii)-intermediate engaging pendant alkenes in a Heck-like manner. This perspective article commences with an historical overview of the area, which stem...

The carbon-carbon bond forming process is one of the most important transformations in organic synthesis aimed at the construction of complex molecules. In this regard, the Heck reaction poses as a pivotal synthetic methodology widely used for the formation of carbon-carbon bonds starting from olefins and an electrophile. An alternative of growing importance to the conventional Heck reaction wa...

Macrocyclization is typically the key step in syntheses of cyclophane-type natural products. Considering compounds with axially chiral biaryl moieties, control atroposelectivity essential for biological activity and synthetically challenging. Herein we report on atroposelective macrocyclization involving an oxidative Heck type process enabling first atropo-enantiopure synthesis isoriccardin C. ...

With the goal of avoiding the need for anhydride additives, the catalytic decarbonylation of p-nitrophenylesters of aliphatic carboxylic acids to their corresponding olefins, including commodity monomers like styrene and acrylates, has been developed. The reaction is catalyzed by palladium complexes in the absence of added ligands and is promoted by alkali/alkaline-earth metal halides. Combinat...

Abstract: A reusable PdCl2(NH3)2/cationic 2,2′-bipyridyl system was used to catalyze the double Mizoroki-Heck reaction of aryl iodides with electron-deficient alkenes in water in the absence of inert gas, giving β,β-diarylated carbonyl derivatives in good to excellent yields. The formation of unsymmetrical β,β-diarylated alkenes were also studied by coupling aryl iodides with the corresponding ...