Dichloro-bis(aminophosphine) complexes of palladium: highly convenient, reliable and extremely active suzuki-miyaura catalysts with excellent functional group tolerance.

Jeanne L Bolliger, Christian M Frech

Index: Chemistry 16(13) , 4075-81, (2010)

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Abstract

Dichloro-bis(aminophosphine) complexes are stable depot forms of palladium nanoparticles and have proved to be excellent Suzuki-Miyaura catalysts. Simple modifications of the ligand (and/or the addition of water to the reaction mixture) have allowed their formation to be controlled. Dichlorobis[1-(dicyclohexylphosphanyl)piperidine]palladium (3), the most active catalyst of the investigated systems, is a highly convenient, reliable, and extremely active Suzuki catalyst with excellent functional group tolerance that enables the quantitative coupling of a wide variety of activated, nonactivated, and deactivated and/or sterically hindered functionalized and heterocyclic aryl and benzyl bromides with only a slight excess (1.1-1.2 equiv) of arylboronic acid at 80 degrees C in the presence of 0.2 mol % of the catalyst in technical grade toluene in flasks open to the air. Conversions of >95 % were generally achieved within only a few minutes. The reaction protocol presented herein is universally applicable. Side-products have only rarely been detected. The catalytic activities of the aminophosphine-based systems were found to be dramatically improved compared with their phosphine analogue as a result of significantly faster palladium nanoparticle formation. The decomposition products of the catalysts are dicyclohexylphosphinate, cyclohexylphosphonate, and phosphate, which can easily be separated from the coupling products, a great advantage when compared with non-water-soluble phosphine-based systems.