Photoinduced Cobalt Catalysis for the Reductive Coupling of Pyridines and Dienes Enabled by Paired Single‐Electron Transfer**

Selective hydroarylation of dienes has potential to provide swift access to useful building blocks. However, most existing methods rely on dienes stabilised by an aromatic group and transmetallation or nucleophilic attack steps require electron-rich aryl coupling partners. As such, there are few examples which tolerate wide-spread heteroarenes such as pyridine. Whilst allylic C-H functionalisation could be considered an alternative approach, the positional selectivity of unsymmetrical substrates is hard to control. Here, we report a general approach for selective hydropyridylation of dienes under mild conditions using metal catalysed hydrogen-atom transfer. Photoinduced, reductive conditions enable simultaneous formation of a cobalt-hydride catalyst and the persistent radical of easily-synthesised pyridyl phosphonium salts. This facilitates selective coupling of dienes in a traceless manner at the C4-position of a wide-range of pyridine substrates. The mildness of the method is underscored by its functional-group tolerance and demonstrated by applications in late-stage functionalisation. Based on a combination of experimental and computational studies, we propose a mechanistic pathway which proceeds through non-reversible hydrogen-atom transfer (HAT) from a cobalt hydride species which is uniquely selective for dienes in the presence of other olefins due to a much higher relative barrier associated with olefin HAT.