Intermediate compounds 3a-d have been produced by aldolization/crotonization in the presence of freshly prepared sodium ethanolate in moderate to good yields (from 38 to 59%). The deprotection of the aryl-γ-pyrone units in acidic medium leads to the first family of oxoderivatives, compounds 4a-d, in excellent yields (>80%) (Scheme 1). Scheme 1. Synthetic pathway leading to the biomimetic oxo-photoswitches, biomimetic analogs of CC Those later were also used as building blocks to synthesize the second family of compounds bearing a malonitrile acceptor group (Scheme 2). The compounds 5a-d were obtained by Knoevenagel condensation in acetic anhydride medium with excellent yields (>80%) except for the derivative bearing the dimethylamine moiety (5d, 54%). Their deprotection under mild basic conditions provided the malonitrile family of compounds 6a-d (Scheme 2).