(11bS)-4-Mercapto-2,6-bis(2,4,6-triisopropylphenyl)dinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepine 4-oxide is a chiral phosphoric acid catalyst for a variety of enantioselective transformations, especially for carbon-carbon and carbon-heteroatom bond-forming reactions.