Wittig-type Reaction of Dimetallated Carbodianion Species as Produced by Zinc Reduction of gem-Polyhalogen Compounds in the Presence of Lewis Acids

Abstract
Treatment of R1COR2 with a suspension prepared from diiodomethane, trimethylaluminum and excess zinc in tetrahydrofuran at room temperature affords olefins R1R2C=CH2 in fair (R1,R2=alkyl) to good (R1=alkyl, R2=H) yields. The ketone methylenation is better carried with another system consisting of CH2Br2–Zn–TiCl4. Ketones and aldehydes are transformed into α-chloro α,β-unsaturated esters or α,β-unsaturated esters in good yields on treatment with methyl trichloroacetate or t-butyl dichloroacetate (ethyl dibromoacetate) in the presence of diethylaluminum chloride and zinc.