Recoverable Palladium-Catalyzed Carbon-Carbon Bond Forming Reactions under Thermomorphic Mode: Stille and...

The reaction of [PdCl₂(CH₃CN)₂] and bis-4,4'-(R_fCH₂OCH₂)-2,2'-bpy (1a-d), where R_f = n-C₁₁F₂₃ (a), n-C₁₀F₂₁ (b), n-C₉F₁₉ (c) and n-C₈F₁₇ (d), respectively, in the presence of dichloromethane (CH₂Cl₂) resulted in the synthesis of Pd complex, [PdCl₂[4,4'-bis-(R_fCH₂OCH₂)-2,2'-bpy] (2a-d). The Pd-catalyzed Stille arylations of vinyl tributyltin with aryl halides were selected to demonstrate the feasibility of recycling usage with 2a as the catalyst using NMP (N-methyl-2-pyrrolidone) as the solvent at 120-150 °C. Additionally, recycling and electronic effect studies of 2a-c were also carried out for Suzuki-Miyaura reaction of phenylboronic acid derivatives, 4-X-C₆H₄-B(OH)₂, (X = H or Ph) with aryl halide, 4-Y-C₆H₄-Z, (Y = CN, H or OCH₃; Z = I or Br) in dimethylformamide (DMF) at 135-150 °C. At the end of each cycle, the product mixtures were cooled to lower temperature (e.g., -10 °C), and then catalysts were recovered by decantation with Pd leaching less than 1%. The products were quantified by gas chromatography/mass spectrometry (GC/MS) analysis or by the isolated yield. The complex 2a-catalyzed Stille reaction of aryl iodides with vinyl tributyltin have good recycling results for a total of 8 times, with a high yield within short period of time (1-3 h). Similarly, 2a-c-catalyzed Suzuki-Miyaura reactions also have good recycling results. The electronic effect studies from substituents in both Stille and Suzuki-Miyaura coupling reactions showed that electron withdrawing groups speed up the reaction rate. To our knowledge, this is the first example of recoverable fluorous long-chained Pd-catalyzed Stille reactions under the thermomorphic mode.