Êtes-vous un étudiant de l'EPFL à la recherche d'un projet de semestre?
Travaillez avec nous sur des projets en science des données et en visualisation, et déployez votre projet sous forme d'application sur Graph Search.
We report in this paper a Pd(II)-catalyzed migratory gem-fluorolactonization of ene-carboxylic acids. Reaction of 4-methylenealkanoic acid derivatives with Selectfluor in the presence of Pd(OAc)2 (1.0 mol %) at room temperature affords fluorolactones in good to excellent yields. 2-(2-Meth- ylenecycloalkanyl)acetic acids are transformed to bridged fluorolactones under identical conditions. One C C, one C O and one tertiary C F bond were generated along the gem-disubstituted carbon-carbon double bond in this operationally simple transformation. Trapping experiments indicates that the reaction is initiated by a 5-exo-trig oxypalladation followed by Pd oxidation, regioselective ring-enlarging 1,2-alkyl/Pd(IV) dyotropic rearrangement and C F bond forming reduc- tive elimination cascade. Post-transformations of these fluorolactones taking advantage of the electrophilicity of the 1-fluoroalkylcarboxylate function are also docu- mented.
Rosario Scopelliti, Shiori Fujimori
, , ,
Jérôme Waser, Eliott Hugo Joran Le Du, Julien Aymeric Borrel