Water-Promoted Ir-Catalyzed Ring-Opening of Oxa(aza)benzonorbornadienes with Fluoroalkylamines.

A highly effective water-promoted iridium-catalyzed ring-opening reaction of oxa(aza)benzonorbornadienes with fluoroalkylamines was developed for the synthesis of fluorinated trans-1,2-amino alcohol or diamine derivatives. Tetrabutylammonium iodide (TBAI) was necessary as an additive for excellent yields in the presence of [Ir(COD)Cl]2 catalyst. Fluorinated trans-1,2-amino alcohol or diamine derivatives could be obtained in good to excellent yields (up to 98%) under mild conditions within a shorter period. Another interesting finding was that the addition of water could greatly enhance the ring-opening reaction. In addition, a plausible mechanism for the ring-opening reaction was proposed.