Catalytic asymmetric intramolecular homologation of ketones with α-diazoesters: synthesis of cyclic α-aryl/alkyl β-ketoesters

Abstract

A catalytic asymmetric intramolecular homologation of simple ketones with α-diazoesters was firstly accomplished with a chiral N,N'-dioxide-Sc(OTf)3 complex. This method provides an efficient access to chiral cyclic α-aryl/alkyl β-ketoesters containing an all-carbon quaternary stereocenter. Under mild conditions, a variety of aryl- and alkyl-substituted ketone groups reacted with α-diazoester groups smoothly through an intramolecular addition/rearrangement process, producing the β-ketoesters in high yield and enantiomeric excess.

Keywords: asymmetric catalysis; homologation; scandium; α-diazoesters; β-ketoesters.