Stereoselective Halo-Succinimide Facilitated α-Halogenations of Substituted α-Trialkylsilyl-β-Substituted-α,β-Unsaturated Esters

The NXS (X = Cl, Br)-mediated halogenation of a series of (E)-α-trimethylsilyl-β-alkyl(aryl)-α,β-unsaturated esters in dimethylformamide (DMF) has furnished (Z)-β-substituted-α-halogenated-α,β-unsaturated ester products in moderate to high isolated yields (58-90%) with dr values of >20:1 coupled with the inversion of olefin stereochemistry. The reaction process was hypothesized to include an initial halonium cation intermediate, followed by regioselective ring opening with DMF. Subsequent anti-E2-type concomitant elimination allowed for the stereoselective formation of the product vinylic bromo-and chloroesters.