The benzoin reaction, the coupling of two aromatic aldehydes [Eq.(1)], is one of the most important transformations catalyzed by N-heterocyclic carbenes (NHCs).[1] It proceeds through a unique umpolung strategy, which is widely used to provide unconventional access to various target molecules.[2] Intriguingly, however, in most cases this strategy is limited to aldehydes,[3] and the umpolung of other electrophiles in this realm of NHC ...