Asymmetric Synthesis of Fluorinated Isoindolinones through Palladium‐Catalyzed Carbonylative Amination of Enantioenriched Benzylic Carbamates. Issue 32 (29th June 2015)

• Record Type: Journal Article
• Authors: Barrio, Pablo; Ibáñez, Ignacio; Herrera, Lidia; Román, Raquel; Catalán, Silvia; Fustero, Santos
• Is Part Of: Chemistry. Volume 21:Issue 32(2015)
• Page Start: 11579
• Page End: 11584
• Publication Date: 2015-06-29
• Subjects: asymmetric synthesis -- carbonylation -- fluorine -- heterocycles -- palladium; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201500773
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: The asymmetric synthesis of fluorinated isoindolinones has been achieved by a palladium‐catalyzed aminocarbonylation reaction of the corresponding α‐fluoroalkyl o ‐iodobenzylamines. A base‐mediated anti β‐hydride elimination process was suggested to explain the partial erosion of the optical purity observed in some cases. This mechanistic rationale enabled the minimization of this partial racemization by fine‐tuning the p K a of the base. Abstract : Basic space : The asymmetric synthesis of fluorinated isoindolinones has been achieved by a palladium‐catalyzed aminocarbonylation reaction of the corresponding α‐fluoroalkyl o ‐iodobenzylamines (see figure; PG=protecting group). A base‐mediated anti β‐hydride elimination process was suggested to explain the partial erosion of the optical purity observed in some cases. This mechanistic rationale enabled the minimization of this partial racemization by fine‐tuning the p K a of the base.