A tungsten-catalyzed allylic allylation of sodium sulfinate as the heteroatom nucleophile was developed. The reaction utilizes inexpensive and readily available (CH3CN)3W(CO)3 as a precatalyst and proceeds at 60 °C temperature in the presence of 2,2'-bipyridine and its derivatives as ligand. The synthetic utility of allylic sulfones as electrophile was further demonstrated through Suzuki-Miyaura cross-coupling as showcased by the formal synthesis of (±)-hinokiresinol.