Skeletal Transformation Triggered by C-F Bond Activation after Photochemical Rearrangement of Fluorinated [7]Helicenes

Chemistry. 2022 Apr 1;28(19):e202200132. doi: 10.1002/chem.202200132. Epub 2022 Mar 4.


Tri- and tetra-fluorinated [7]helicenes are photolabile and undergo a double fluorine atom transfer. Herein, we show that the transferred product further undergoes a skeletal transformation on silica gel. The transformation begins with activation of the allylic C-F bond on the silanol surface. Then, the resulting carbocation readily undergoes a regioselective nucleophilic aromatic substitution with water, depending on the position of the fluorine substituents. Hexafluoro-2-propanol also activated the allylic C-F bond and acted as a nucleophile. These findings support the generation of a highly reactive cationic electrophilic intermediate in the successive transformations involving fluorine atoms.

Keywords: C−F bond activation; aromatic substitution; carbocations; domino reactions; fluorine.