Discovery of a simple iron catalyst reveals the intimate steps of C-H amination to form C-N bonds.

A clear trend of declining yields after 3 and 24 h was observed from tertiary to secondary and primary C–H bonds (11a, 12a, and 13a, respectively), which mirrors the increased C–H BDE (entries 2–4). 73 This trend suggests that either C–H bond activation becomes rate-limiting for those substrates, or that product coordination is more effective due to the stronger coordination ability of these aliphatic pyrrolidines.

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