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.

Key words

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).