Chiral Sulfide Catalysis for Desymmetrizing Enantioselective Chlorination

An unprecendented chiral sulfide catalyzed desymmetrizing enantioselective chlorination is disclosed. Various aryl-tethered diolefins and diaryl-tethered olefins afforded teralins and tricyclic hexahydrophenalene derivatives, respectively, bearing multiple stereogenic centers in high yields with excellent enantio- and diastereoselectivities. In contrast, the tertiary amine catalyst (DHQD)(2)PHAL led to a diastereomeric product. The products could be transformed into a variety of compounds, such as spiro-N-heterocycles.