Exercise in 1-aryl-3-CF₃-1<i>H</i>-pyrazoles: regioselective synthesis of 4-/5-iodides and cross-coupling reactions

A series of 1-aryl-3-CF₃-1<i>H</i>-pyrazoles was prepared and examined using iodination reactions. Treatment with <i>n</i>-BuLi followed by trapping of the corresponding lithium pyrazolide with elemental iodine produced 5-iodo derivatives exclusively, while CAN-mediated iodination with I₂ afforded isomeric 4-iodides in a highly regioselective manner. The title iodides were demonstrated to be convenient building blocks for the preparation of more complex 3-trifluoromethylated pyrazoles through the model Suzuki-Miyaura and Sonogashira reactions.