02133nas a2200181 4500008004100000022001400041245011000055210006900165260011000234300001400344490000600358520136900364100001901733700003001752700001901782700002601801856012401827 2013 eng d a2044-475300aHydroxyapatite supported palladium catalysts for suzuki-miyaura cross-coupling reaction in aqueous medium0 aHydroxyapatite supported palladium catalysts for suzukimiyaura c aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcMAR a1625-16330 v33 a
Supported palladium catalyst 1 has been prepared by the immobilisation of [Pd(COD)Cl-2] (COD = 1,5-cyclooctadiene) on hydroxyapatite. Catalyst 2 has been prepared by subsequent reduction of catalyst 1 with sodium borohydride in ethanol. Under similar reaction conditions, catalyst 1 with Pd2+, is found to be almost five times more active than 2. Using 1 as the catalyst and water as the solvent, reaction conditions for Suzuki-Miyaura cross-coupling reactions have been optimised under aerobic conditions. The best catalytic activities are observed in the presence of potassium carbonate as the base and tetrabutylammonium bromide as a promoter. Catalyst 1 has been tested for catalytic cross-coupling reactions with sixteen different, electronically neutral, electron rich, electron poor and sterically hindered aryl boronic acids, and several different aryl halides including aryl chlorides. More than thousand turnovers and high selectivities to the hetero-coupled products have been observed in most cases. For many substrates the turnovers with 1 are notably more than what has been reported with other supported catalysts in water. The recyclability and scale-up potential of catalyst 1 have been tested and found to be satisfactory. A negligible drop in activity is observed over ten recycles with an accumulated turnover number of similar to 30000.
1 aIndra, Arindam1 aGopinath, Chinnakonda, S.1 aBhaduri, Sumit1 aLahiri, Goutam, Kumar uhttp://library.ncl.res.in/content/hydroxyapatite-supported-palladium-catalysts-suzuki-miyaura-cross-coupling-reaction-0