Zirconium/Nickel‐Mediated One‐Pot Ketone Synthesis

A zirconium/nickel‐mediated one‐pot synthesis of ketones is reported. In the presence of Zn or Mn, Cp 2 ZrCl 2 was found to dramatically accelerate the coupling and suppress side product formation via an I→SPy displacement at the same time. Unlike Zn/Pd‐ and Fe/Cu‐mediated one‐pot ketone syntheses, the new method is effective for nucleophiles bearing OR or equivalent functional groups at the α‐position. A mechanism comprising a nickel catalytic cycle, a zirconium catalytic cycle, and Zr→Ni transmetalation is proposed, and Cp 2 ZrCl 2 and/or low‐valent Zr species are suggested to play crucial dual roles.