Suzuki Coupling Reactions of Heteroarylboronic Acids with Aryl Halides and Arylboronic Acids with Heteroaryl Bromides Using a Tetraphosphine/Palladium Catalyst

Abstract

cis,cis,cis-1,2,3,4-Tetrakis(diphenylphosphinomethyl)cyclopentane/[PdCl(C₃H₅)]₂ efficiently catalyses the Suzuki reaction of heteroarylboronic acids with aryl bromides and also the coupling of arylboronic acids with heteroaryl bromides. The coupling of thiopheneboronic acids, 3-furanboronic acid and 3-pyridineboronic acid with a variety of aryl bromides gave the corresponding adducts in good yields. However, in most cases, ­better results in terms of substrate/catalyst ratio were obtained for the reaction of heteroaryl bromides with arylboronic acids.

Key words

heteroaryl bromides - arylboronic acids - Suzuki reaction - heteroarylboronic acids

References

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21

A typical experiment (Table [1] , entry 11): Thiophene-3-boronic acid (0.256 g, 2 mmol), 4-bromo-acetophenone (0.199 g, 1 mmol) and K₂CO₃ (0.276 g, 2 mmol) at 130 °C over 20 h in xylene (3 mL) in the presence of cis,cis,cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane/[PdCl(C₃H₅)]₂ complex (0.004 mmol) under argon afforded the corresponding product after evaporation and filtration through silica gel; yield: 0.156 g, 77%. ¹H NMR (300 MHz, CDCl₃): δ = 7.98 (d, 2 H, J = 8.3 Hz), 7.68 (d, 2 H, J = 8.3 Hz), 7.57 (dd, 1 H, J = 2.5, 1.7 Hz), 7.43-7.40 (m, 2 H), 2.61 (s, 3 H).