Easy and mild fluoride-mediated direct mono- and dialkoxylation of perylenediimides

•A new reaction for the mono- and dialkoxylation of the perylenediimide is described.•The fluoride-promoted reaction takes place in the bay positions.•The reaction can be applied to bromoperylenediimides.

The reaction of perylenediimides with alcohols in the presence of fluoride anions yields 1-alkoxy- or 1,6(7)-dialkoxyperylenediimides under very mild metal-free conditions. The reaction can also be applied to bay- and ortho-brominated perylenediimides.

Graphical abstractF−is the key: A metal-free methodology for the selective direct alkoxylation of the perylenediimide bay-positions has been developed by using fluoride ions which act as electron donors.Figure optionsDownload full-size imageDownload as PowerPoint slide