Catalytic Enantioselective Cloke–Wilson Rearrangement. (4th June 2018)

• Record Type: Journal Article
• Authors: Ortega, Alesandere; Manzano, Rubén; Uria, Uxue; Carrillo, Luisa; Reyes, Efraim; Tejero, Tomas; Merino, Pedro; Vicario, Jose L.
• Is Part Of: Angewandte Chemie. Volume 130:Number 27(2018)
• Page Start: 8357
• Page End: 8361
• Publication Date: 2018-06-04
• Subjects: Asymmetrische Katalyse -- Carbokationen -- Gespannte Moleküle -- Organokatalyse -- Umlagerungen; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201804614
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Racemic cyclopropyl ketones undergo enantioselective rearrangement to deliver the corresponding dihydrofurans in the presence of a chiral phosphoric acid as the catalyst. The reaction involves activation of the donor‐acceptor cyclopropane substrate by the chiral Brønsted acid catalyst to promote the ring‐opening event, thus generating a carbocationic intermediate that subsequently undergoes cyclization. Computational studies and control experiments support this mechanistic pathway.