Homogeneous and Gas–Liquid Catellani‐Type Reaction Enabled by Continuous‐Flow Chemistry

A practical homogeneous and gas‐liquid palladium‐catalyzed Catellani‐type reaction using a continuous‐flow platform is described. The implementation of continuous‐flow technology allowed the acceleration of the transformation and, for the first time, expansion of the chemical space to gaseous olefins (i.e., ethylene, propylene and 3,3,3‐trifluoropropene), thus providing a safe and practical approach to sterically hindered ortho‐disubstituted styrenes and vinyl arenes. The complete control over the stoichiometry of gaseous reagents through flow technology proved essential for directing the selectivity of the Catellani reaction to the desired products.