Key Mechanistic Features of the Silver(I)-Mediated Deconstructive Fluorination of Cyclic Amines: Multistate
Jose B Roque1, Richmond Sarpong1, Djamaladdin G Musaev2
1Department of Chemistry, University of California, Berkeley, California 94720, United States.
Abstract:
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.
Related Concept Videos
Electrophilic Aromatic Substitution: Fluorination and Iodination of Benzene
Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions
E1 Reaction: Kinetics and Mechanism
ortho–para-Directing Deactivators: Halogens
Limitations of Friedel–Crafts Reactions
Preparation of Amines: Reductive Amination of Aldehydes and Ketones


