Palladium Catalysed Cross-Coupling of Aryl Bromides with Functionalised Arylboronic Acids in the Presence of a Tetraphosphine Ligand

Abstract

Cis,cis,cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)- cyclopentane/[PdCl(C₃H₅)]₂ system catalyses efficiently the cross-coupling of aryl bromides with functionalised arylboronic acids. The electronic properties of the arylboronic acids seem to have a minor influence on the reaction rate. Better results were generally obtained for the reaction of electron poor aryl bromides associated with electron rich arylboronic acids rather than the contrary.

catalysis - palladium - tetraphosphine - arylboronic acids - aryl bromides

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8

As a typical experiment, the reaction of 4-bromoaceto phenone (1.99 g, 10 mmol), 4-methoxybenzeneboronic acid (3.04 g, 20 mmol) and K₂CO₃ (2.8 g, 20 mmol) at 130 °C during 20 h in dry xylene (10 mL) in the presence of cis,cis,cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclo-pentane/[PdCl(C₃H₅)]₂ complex (0.00001 mmol) under argon affords the corresponding adduct after extraction with dichloromethane, evaporation and filtration on silica gel (dichloromethane/diethyl ether: 1/5) in 80% (1.81 g) isolated yield. ¹H NMR (300 MHz, CDCl₃): δ = 8.00 (d, J = 8.5 Hz, 2 H), 7.64 (d, J = 8.5 Hz, 2 H), 7.56 (d, J = 8.7 Hz, 2 H), 6.99 (d, J = 8.7 Hz, 2 H), 3.85 (s, 3 H), 2.62 (s, 3 H).