(3aR,8aR)-Tetrahydro-6-hydroxy-2,2-dimethyl-4,4,8,8-tetra-2-naphthalenyl-6-oxide-1,3-dioxolo[4,5-e][1,3,2]dioxaphosphepin is a chiral phosphoric acid catalyst for a variety of enantioselective transformations, especially for carbon-carbon and carbon-heteroatom bond-forming reactions.