Copper catalyzed multi-functionalization of unsaturated carbon-carbon bonds is a powerful tool for the generation of complex molecules. We report a regiodivergent process that allows a switch between 1,4-borocupration and 4,1-borocupration of 1,3-dienes upon a simple change in ligand. The subsequently generated allyl coppers are trapped in an electrophilic cyanation to selectively generate densely functionalized and synthetically versatile 1,2- or 4,3-borocyanation products.

Copper catalyzed multi‐functionalization of unsaturated carbon‐carbon bonds is a powerful tool for the generation of complex molecules. We report a regiodivergent process that allows a switch between 1,4‐borocupration and 4,1‐borocupration of 1,3‐dienes upon a simple change in ligand. The subsequently generated allyl coppers are trapped in an electrophilic cyanation to selectively generate densely functionalized and synthetically versatile 1,2‐ or 4,3‐borocyanation products.

SmI2-catalyzed radical cascade cyclizations were used to generate complex carbocyclic products bearing quaternary stereocenters with high selectivity. Bicyclic scaffolds containing four contiguous stereocenters and one quaternary stereocenter were obtained in excellent yields (up to 99%) and with high diastereocontrol by using 5 mol% of SmI2 at ambient temperature in the absence of co-reductants or additives. Mechanistic studies support a radical relay mechanism.