Direct Cyclization of Tertiary Aryl Amines with Iodonium Ylides

Described herein is a direct cyclization of simple tertiary aryl amines with iodonium ylides leading to a broad range of N‐heterocycles. Completely different from the known reactivity of iodonium ylides, the finding reported herein is that an iodonium ylide is capable of cleaving a C(sp 3 )−H bond and accepting two hydrogen atoms of a tertiary aryl amine, thus inducing a novel cyclization process. This transformation can proceed without the assistance of a transition‐metal catalyst and eliminates the need for the premodification of the amine or the use of an additional initiator/oxidant.