New Class of Electrophiles in Palladium/Norbornene Cooperative Catalysis: Sulfenamide-Enabled Ortho Thiolation of Aryl Iodides

To expand the synthetic platform of the palladium-norbornene cooperative catalysis, here we report a general ortho thiolation of aryl and heteroaryl iodides using sulfenamides as a new class of electrophiles. The sulfenamides derived from a ε-tbutyl-lactam were found most efficient to introduce various aryl and methyl sulfur groups at the arene ortho position. The ipso functionalization is achieved through Heck or Suzuki termination. This reaction also provides a convenient access to the corresponding aryl sulfoxides and sulfones via selective oxidation of the ortho thiolation products.