Dependence of the reactivities of titanium enolates on how they are generated: Diastereoselective coupling of phenylacetic acid esters using titanium tetrachloride

Oxidative coupling of phenylacetic acid esters was easily achieved by treating the esters with TiCl4 and then adding Et(3)N to the resulting solution. The products consisted of dl- and meso-2,3-diphenylsuccinic acid esters with the Claisen condensation product, and the ratio of these products depended on the reaction conditions. Reaction conditions suitable for high db selectivity were determined, and a dimer of titanium enolate was postulated as an intermediate responsible for the high db selectivity. The selectivities were compared with those in known oxidative couplings in which titanium enolate intermediates are prepared through lithium enolates and silyl enol ethers. The results suggest that the reactivities of titanium enolates intermediates depend on how they are generated.