Valence Tautomerism in Titanium Enolates: Catalytic Radical Haloalkylation and Application in the Total Synthesis of Neodysidenin

A direct ruthenium-catalyzed radical chloroalkylation of N-acyl oxazolidinones capitalizing on valence tautomerism of titanium enolates has been developed. The chloroalkylation method served as the centerpiece in the enantioselective total synthesis of trichloroleucine-derived marine natural product neodysidenin.