TY - JOUR
AU1 - Petzold, Daniel
AU2 - Nitschke, Philipp
AU3 - Brandl, Fabian
AU4 - Scheidler, Veronica
AU5 - Dick, Bernhard
AU6 - Gschwind, Ruth M.
AU7 - König, Burkhard
AB - The first example for the photocatalytic generation of a highly electrophilic intermediate that is not based on radical reactivity is reported. The single‐electron reduction of bench‐stable and commercially available 4‐(trifluoromethoxy)benzonitrile by an organic photosensitizer leads to its fragmentation into fluorophosgene and benzonitrile. The in situ generated fluorophosgene was used for the preparation of carbonates, carbamates, and urea derivatives in moderate to excellent yields via an intramolecular cyclization reaction. Transient spectroscopic investigations suggest the formation of a catalyst charge‐transfer complex‐dimer as the catalytic active species. Fluorophosgene as a highly reactive intermediate, was indirectly detected via its next downstream carbonyl fluoride intermediate by NMR. Furthermore, detailed NMR analyses provided a comprehensive reaction mechanism including a water dependent off‐cycle equilibrium.
TI - Visible‐Light‐Mediated Liberation and In Situ Conversion of Fluorophosgene
JF - Chemistry - A European Journal
DO - 10.1002/chem.201804603
DA - 2019-02-02
UR - https://www.deepdyve.com/lp/wiley/visible-light-mediated-liberation-and-in-situ-conversion-of-cTahC56kXp
SP - 361
EP - 366
VL - 25
IS - 1
DP - DeepDyve
ER -