Brook Rearrangement as a Trigger for the Ring Opening of Strained Carbocycles. (14th December 2015)

• Record Type: Journal Article
• Authors: Zhang, Fa‐Guang; Eppe, Guillaume; Marek, Ilan
• Is Part Of: Angewandte Chemie. Volume 128:Number 2(2016)
• Page Start: 724
• Page End: 728
• Publication Date: 2015-12-14
• Subjects: Brook‐Umlagerung -- Ein‐Topf‐Reaktionen -- Gespannte Moleküle -- Quartäre Kohlenstoffzentren -- Synthesemethoden; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201510094
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: The combined regio‐ and stereoselective carbometalation of cyclopropenyl amides, followed by the addition of an acyl silane, led to the formation of polysubstituted cyclopropyl derivatives as unique diastereoisomers. Upon warming of the reaction mixture to room temperature, a Brook rearrangement proceeded with inversion of configuration to provide ready access to δ‐ketoamides possessing a quaternary carbon center with high enantiomeric ratios through selective CC bond cleavage of the ring.