Practical Metal-Free C(sp<sup>3</sup>)H Functionalization: Construction of Structurally Diverse α-Substituted<i>N</i>-Benzyl and<i>N</i>-Allyl Carbamates
is a practical and universal CH functionalization of readily removable N‐benzyl and N‐allyl carbamates, with a wide range of nucleophiles at ambient temperature promoted by Ph3CClO4. The metal‐free reaction has an excellent functional‐group tolerance, and displays a broad scope with respect to both N‐carbamates and nucleophile partners (a variety of organoboranes and CH compounds). The synthetic utility