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The efficiency and simplicity of cross-dehydrogenative-coupling (CDC) reactions have captured the imagination of the organic chemical community. If we are to understand and predict these processes we must understand how they work. This chapter outlines what is known of the mechanisms of metal-catalyzed, metal-free and photo-induced CDC reactions. While much remains to be understood, and the reaction scope is still narrow, there is accumulating evidence on the nature of electron and atom transfer in these oxidative couplings and why these result in one dominant reaction pathway from a large number of available outcomes in such one-pot processes.

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