Auto‐Tandem Catalysis: PdII‐Catalysed Dehydrogenation/Oxidative Heck Reaction of Cyclopentane‐1,3‐diones

Abstract A Pd II catalyst system has been used to successfully catalyse two mechanistically distinct reactions in a one‐pot procedure: dehydrogenation of 2,2‐disubstituted cyclopentane‐1,3‐diones and the subsequent oxidative Heck coupling. This auto‐tandem catalytic reaction is applicable to both batch and continuous flow processes, with the latter being the first example of a tandem aerobic dehydrogenation/oxidative Heck in flow. In addition, a telescoped reaction involving enantioselective desymmetrisation of the all‐C quaternary centre was successfully achieved.