Titanium-mediated chelation-controlled aldol type reactions of acetate thioimide enolates with representative aldehydes proceed with high n-facial differentiation. An investigation of the influence of the nature of the imide enolate ligands and the Lewis acids in the non- chelation-controlled aldol bond construction process of acetate imide enolates reveals that alternation of either the boryl geometry or imide enolate ligand leads to n-facial selectivity ...