A Cu/Pd-catalyzed allylboration of alkynes with allyl carbonates and bis(pinacolato)diboron to afford borylated skipped dienes is reported. Synergistic Cu and Pd catalysis enables this protocol to work for a wide array of alkynes and allyl carbonates under mild conditions with total regio-and stereocontrol. This transformation features the catalytic generation of βborylalkenylcopper intermediates and their use in Pd-catalyzed allylic substitution of allyl carbonates. The utility of this method is highlighted by the synthesis of (Z,E)-α-homofarnesene (pheromone) and the terpenoid precursor of Merochlorins (potent antibiotic agents).

The first copper‐catalyzed enantioselective allylboration of alkynes is reported. The method employs a multitasking chiral NHC‐Cu catalyst and provides access to densely functionalized molecules from simple starting materials with excellent levels of chemo‐, regio‐, and enantioselectivity. These multifunctional products display highly versatile reactivity as shown by the synthesis of a variety of non‐racemic molecular scaffolds. DFT calculations were conducted to gain insight into the high selectivity levels of this catalytic process.

A new family of cationic, bidentate (P^N)gold(III) fluoride complexes has been prepared and a detailed characterization of the gold‐fluoride bond has been carried out. Our results correlate with the observed reactivity of the fluoro ligand, which undergoes facile exchange with both cyano and acetylene nucleophiles. The resulting (P^N)arylgold(III)C(sp) complexes have enabled the first study of reductive elimination on (P^N)gold(III) systems, which demonstrated that C(sp2)−C(sp) bond formation occurs at higher rates than those reported for analogous phosphine‐based monodentate systems.