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During the last decades, we have witnessed a great improvement of dual catalytic processes, where photocatalysis is combined with transition-metal catalysis. With this approach, many new chemical transformations can be accomplished, which are impossible or not easily accessible through a single catalytic cycle. From a general point of view, dual catalysis consists in a visible-light mediated single electron transfer process (SET) that is responsible for the oxidation or reduction of a transition-metal complex intermediate. Palladium-, nickel-, copper- and gold-catalyzed organic reactions are the main areas where dual catalysis can find advantageous applications. Limiting the discussion to palladium-catalyzed reactions, the combination with photoredox processes has been exploited in C(sp2)–H activation and functionalization, in allylation reactions, in dehydrogenation of saturated hydrocarbons and nitrogen-containing heterocycles or even in the oxidation of lignin and related complex systems. All these transformations, however, require that palladium always reacts in its ground state and does not interact directly with light.

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