Synthesis of Dithia[5]helicenes and Enantioselective Synthesis of Helically Chiral Thia[6]helicenes via Rh-Catalyzed Intramolecular [2 + 2 + 2] Cycloaddition of Triynes.

Dithia[5]helicenes and helically chiral thia[6]helicenes were synthesized in high yields via a cationic Rh-catalyzed intramolecular [2 + 2 + 2] cycloaddition of triynes bearing sulfur-containing 1,6-diynes. Thia[6]helicene could be obtained with a high enantiomeric excess of P -isomers by using ( S )-SEGPHOS as a chiral ligand. This protocol is the first example of the synthesis of thiahelicenes via [2 + 2 + 2] cycloaddition and can also be used for the asymmetric construction of an aza[6]helical skeleton.