Key Mechanistic Features of the Silver(I)-Mediated Deconstructive Fluorination of Cyclic Amines: Multistate Reactivity versus Single-Electron Transfer

Density functional calculations have provided evidence that a Ag­(I)-mediated deconstructive fluorination of N-benzoylated cyclic amines (LH) with Selectfluor [(F–TEDA)­(BF4)2] begins with an association of the reactants to form a singlet state adduct {[(LH)–Ag]–[F–TEDA]2+}. The subsequent formation of an iminium ion intermediate, [L + –Ag]–HF–[TEDA]+, is, formally, a Ag­(I)-mediated hydride abstraction event that occurs in two steps: (a) a formal oxidative addition (OA) of [F–TEDA]2+ to the Ag­(I) center that is attended by an electron transfer (ET) from the substrate (LH) to the Ag center (i.e., OA + ET, this process can also be referred to as a F-atom coupled electron transfer), followed by (b) H-atom abstraction from LH by the Ag-coordinated F atom. The overall process involves lower-lying singlet and triplet electronic states of several intermediates. Therefore, we formally refer to this reaction as a two-state reactivity (TSR) event. The C–C bond cleavage/fluorination of the resulting hemiaminal intermediate via a ring-opening pathway has also been determined to be a TSR event. A competing deformylative fluorination initiated by hemiaminal to aldehyde equilibration involving formyl H-atom abstraction by a TEDA2+ radical dication, decarbonylation, and fluorination of the resulting alkyl radical by another equivalent of Selectfluor may also be operative in the latter step.