Titanium-Catalyzed Stereoselective Geminal Heterodihalogenation of β-Ketoesters

Abstract

[reaction: see text] beta-Ketoesters can be effectively monofluorinated with F-TEDA using CpTiCl(3) as a catalyst. With the use of this catalyst, the extent of the competing difluorination does not reach 10%. [TiCl(2)(TADDOLato)] complexes catalyze the one-pot enantioselective heterodihalogenation of beta-ketoesters with F-TEDA and NCS to afford alpha-chloro-alpha-fluoro-beta-ketoesters in moderate to good yields. The sequence of addition of the halogenating agents determines the sense of chiral induction.