A synthetic approach towards the cytotoxic polyene polyol macrolide amphidinolide B (1), based on elaboration of the C-1-C-13 carboxylic acid 4 and the C-14-C-25 alcohol 3 units, their esterification to the iodostannyl ester 2, and an intramolecular Stille sp(2)-sp(2) coupling reaction, is described. In spite of adequate precedent and model experiments, circumstances conspired and the aforementioned coupling reaction was not realised in this case. (C) 2000 Elsevier Science Ltd. All rights reserved.