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 <i>ortho</i> thiolation of aryl and heteroaryl iodides using sulfenamides as a new class of electrophiles. The sulfenamides derived from a ε-<i><sup>t</sup></i>butyl-lactam were found most efficient to introduce various aryl and methyl sulfur groups at the arene <i>ortho</i> position. The<i> ipso</i> 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 <i>ortho</i> thiolation products.