Brook Rearrangement as a Trigger for the Ring Opening of Strained Carbocycles

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.

Keywords: Brook rearrangement; one-pot reactions; quaternary carbon centers; strained molecules; synthetic methods.