Metal‐Free Multicatalytic Decarbonylation of Aldehydes Driven by Light

A metal‐free dual photo‐ and organocatalytic decarbonylation of aliphatic aldehydes is described for the first time. On the one hand, a wide range of tertiary aldehydes are smoothly decarbonylated thanks to the combination of thioxanthone as photocatalyst and diphenyl disulfide as organocatalyst. On the other hand, by simply using 4‐CzIPN as photocatalyst instead of thioxanthone, various secondary aldehydes readily undergo decarbonylation in an orthogonal manner, via the in situ formation of 1,4‐dihydropyridines. Both methodologies are compatible with various functional groups and are readily applied to the decarbonylation of complex molecules.