TBHP/Ammonium/Iodide‐Promoted Ring‐Opening of Cyclobutanones toward γ‐Iodo Nitriles

A TBHP/ammonium/iodide‐promoted ring‐opening of a variety of cyclobutanones is developed to access γ‐iodo nitriles in DCM under N 2 at 40 °C. This transformation initiated with in situ imination, forming an iminyl radical that underwent β‐scission to yield a ring‐opening C‐centered radical. The latter successively underwent a single electron transfer followed by nucleophilic substitution, or alternatively proceeded via a halogen‐atom transfer process to generate γ‐iodo nitrile. As such, this mild transition‐metal‐free procedure provides a direct, facile, and efficient pathway toward diverse γ‐iodo functionalized nitriles.