An efficient method for the synthesis of versatile intermediates for biologically interesting 13-deoxy- and 9,13-dideoxyphorbol ester analogs is described. First,more efficient synthetic routes to the bicyclic ketones 7 and 8, which are well-known intermediates for the synthesis of 13-deoxyphorbols, than the previous one were established. Second, 7 and 8 were successfully converted to the intermediates 19, 25 and 27 for the synthesis of 9,13-dideoxyphorbols using Peterson reaction, oxymercuration and nitrile oxide cycloaddition as key steps. (C) 2000 Elsevier Science Ltd. All rights reserved.