Details

Autor(en) / Beteiligte

• Gomez Fernandez, Mario Andrés
• Lefebvre, Corentin
• Sudau, Alexander
• Genix, Pierre
• Vors, Jean‐Pierre
• Abe, Manabu
• Hoffmann, Norbert

Titel

Studies on The Application of The Paternò‐Büchi Reaction to The Synthesis of Novel Fluorinated Scaffolds

Ist Teil von

• Chemistry : a European journal, 2021-11, Vol.27 (63), p.15722-15729

Ort / Verlag

Wiley-VCH Verlag

Erscheinungsjahr

2021

Link zum Volltext

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• In the context of new scaffolds obtained by photochemical reactions, Paternò‐Büchi reactions between heteroaromatic, trifluoromethylphenyl ketone and electron rich alkenes to give oxetanes are described. A comprehensive study has then been carried out on the reaction of aromatic ketones with fluorinated alkenes. Depending on the substitution pattern at the oxetane ring, a metathesis reaction is described as a minor side process to give mono fluorinated alkenes. Overall, this last reaction corresponds to a photo‐Wittig reaction and yield amid isosteres. In order to explain the uncommon regioselectivity of the Paternò‐Büchi reaction with these alkenes, electrostatic‐potential derived charges (ESP) have been determined. In a second computational study, the relative stabilities of the typical 1,4‐diradical intermediates of the Paternò‐Büchi reaction have been determined. The results well explain the regioselectivity. Further transformations of the oxetanes or previous functionalization of the fluoroalkenes open perspectives for oxetanes as core structures for biologically active compounds. New scaffolds obtained by Paternò‐Büchi reactions between heteroaromatic, trifluoromethylphenyl ketone and electron rich or fluorinated alkenes to give corresponding oxetanes. The uncommon regioselectivity with the fluorinated alkenes is explained by the relative stabilities of 1,4‐diradical intermediates of this Paternò‐Büchi reaction. A metathesis (photo‐Wittig reaction) yields amide isosteres.