Ethyl 2‐[(2,6,6‐trimethylbicyclo[3.1.1]heptyl‐3‐yl)methyl]propenoate 2‐(Ethoxycarbonyl)prop‐2‐en‐1‐yl phenyl sulfone Ethyl methacrylate Benzenesulfinic acid, sodium salt (+)‐alpha‐Pinene Catecholborane

A tandem radical process involving conjugate addition to an activated alkene followed by allylation is reported. B‐Alkylcatecholboranes, easily available via hydroboration of the corresponding alkenes, were used to generate the initial radicals. These radicals add efficiently to electrophilic alkenes such as phenyl vinyl sulfone, N‐phenylmaleimide, and dialkyl fumarate. In the last step of this one‐pot process, the radical adducts react with the allylic sulfones. The whole process can be considered as a unique and selective coupling of three different alkenes.

Dedicated to the memory of Professor Hanns Fischer, whose pioneer contribution to radical chemistry remains a fantastic source of inspiration A tandem radical process involving conjugate addition to an activated alkene followed by allylation is reported. B-Alkylcatecholboranes, easily available via hydroboration of the corresponding alkenes, were used to generate the initial radicals. These radicals add efficiently to electrophilic alkenes such as phenyl vinyl sulfone, N-phenylmaleimide, and dialkyl fumarate. In the last step of this one-pot process, the radical adducts react with the allylic sulfones. The whole process can be considered as a unique and selective coupling of three different alkenes.