There is a demand for methodology that can rapidly produce families of catalysts for catalyst-structure-performance studies. The results reported here show microwave accelerated Suzuki coupling of a range of boronic acids with chloro-aryl phosphine-oxides can give high yields of arylated phosphine oxides. Chloro-aryl phosphine-oxide substrates have been found to be unreactive in previous studies, but in these examples, the combination of a highly active (but short lived) catalyst and instantaneous microwave heating at 140 degrees C allows the reactions to proceed. These cross-coupling reactions are being used as the basis for a rapid synthesis of phosphine ligands (readily available by microwave-assisted reduction of the phosphine oxides). (C) 2008 Elsevier B.V. All rights reserved.