Palladium-catalyzed regio- and enantioselective addition of azole heterocycles to alkoxyallenes was developed (up to 92% yields and up to 94% ee). DFT calculations suggest a new Pd(0)-driven mechanistic pathway proceeding through protonation of the Pd-coordinated allene (4-PdL2), which develops a strongly nucleophilic character at the central C atom.

We report on the highly efficient epoxidation of low-molecular-weight and polymeric olefins catalyzed by a supramolecular manganese porphyrin complex using molecular oxygen as an oxidant and an aldehyde as a co-reductant. At ambient temperature and under optimized reaction conditions, the catalyst showed high activity and stereoselectivity. The efficiency of the supramolecular manganese porphyrin was higher than that of a reference porphyrin catalyst, possibly because it was more stable under the applied reaction conditions. Mechanistic studies suggest that a manganese oxo porphyrin complex may be an intermediate in the epoxidation reaction.

A completely regioselective and highly stereoselective palladium‐catalyzed intramolecular hydroarylation of arenesulfonyl ynamines to benzothiazoles was developed. The presence of an electron‐withdrawing group on the triple bond of the sulfonyl ynamine was crucial for the success of the reaction and our mechanistic studies suggest an alkyne‐directed 5‐exo‐dig cyclization pathway. The products easily underwent photoinduced rearrangement to 3‐amino‐1‐benzothiophene‐1,1‐diones (up to 35 % yields after two steps).