Scheme 4.

A) Reaction profiles for the formation of aziridinium 59 from 11. B) Aziridinium ring opening with Et₂NH 8 is immediate. C) Development of a procedure for direct olefin diamination. D) Substrate scope for the direct olefin diamination using a range of different amine and olefin building blocks. [a] A basic work‐up was performed before addition of NaI and the amine. [b] Upon addition of NaI and the amine, the mixture was warmed to 60 °C. [c] In this case the aziridinium was formed using Ag(BF₄). [d] In this case the N‐chloroamine was purified before addition of NaI.* Denotes the minor constitutional isomer.