Occurrence and Synthesis Pathways of (Suspected) Genotoxic α,β-Unsaturated Carbonyls in Chocolate and Other Commercial Sweet Snacks

α,β-Unsaturated carbonyls are highly reactive and described as structural alerts for genotoxicity. Ten of them (either commercially available or synthesized here by combinatorial chemistry) were first investigated throughout the chocolate-making process by solvent-assisted flavor evaporation (SAFE) coupled to GC-MS/SIM. Monitored α,β-unsaturated aldehydes were formed during chocolate production, primarily through aldol condensation of Strecker aldehydes triggered by bean roasting. Notably, levels of 2-phenylbut-2-enal (up to 399 μg·kg–1) and 5-methyl-2-phenylhex-2-enal (up to 216 μg·kg–1) increased up to 40-fold. Dry conching caused evaporation of α,β-unsaturated carbonyls, while wet conching partially restored or increased their levels due to cocoa butter addition. Further analyses showed that α,β-unsaturated aldehydes also occurred in most commercial sweet snacks (up to 16 μg·kg–1), although often at lower concentrations than in roasted cocoa or derived chocolates. In the end, none of the monitored α,β-unsaturated aldehydes did raise a health concern compared to current maximum use levels (2–5 mg·kg–1). On the other hand, much higher levels of genotoxic furan-2(5H)-one were found in crepe and cake samples (up to 4.3 mg·kg–1).