An in situ-generated catalytic system based on PdCl 2 and primary amine-based ligand exhibited excellent activity (up to 98% isolated yield) in the Suzuki-Miyaura cross-coupling reactions of aryl bromides with arylboronic acids in water, at room temperature, without any additive. The efficiencies of the ligands follow the order: (C 6 H 5 ) 3 CNH 2 > C 6 H 5 CH 2 NH 2 > C 6 H 5 NH 2 > C 6 H 11 NH 2 , which is in accordance with the palladacycle forming capacity of the respective ligands. Moderate-to-good yields (up to 78% isolated yield) of the coupling products were also obtained with less reactive aryl chlorides as substrates at room temperature in isopropanol using an alternative protocol based on Pd(OAc) 2 and (C 6 H 5 ) 3 CNH 2 .

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