The synthesis of a range of 5'-deoxy-5'-methylidene phosphonate-containing thymidine dimers has been achieved using a palladium-catalysed cross coupling reaction as a key step. The optimised reaction conditions comprising of palladium acetate, 1,1'-bis(diphenylphosphino)ferrocene and propylene oxide in THF were found to couple a range of N-phosphonates and vinyl bromide 3 in fair to excellent yield. (C) 2000 Elsevier Science Ltd. All rights reserved.