A method for the stereoselective construction of the hemiaminal center in zampanolides

4 p.-1 fig.-1 tab.-i graph. abst.-5 schem.We have developed a new method for the stereoselective establishment of the N-acyl hemiaminal moiety in zampanolide-type structures that involves the reaction of (Z,E)-sorbamide (3) with BINAL-H and subsequent amide transfer froma putative aluminum carboximidoate complex to the aldehyde moiety of a dactylolide precursor, such as 2 or 5. The method has enabled the efficient synthesis of 13-desmethylene-(−)-zampanolide (4), which was found to be an equipotent cell growth inhibitor as the natural product (−)-zampanolide (1).This work was supported by the Swiss National Science Foundation (Projects 200021_149253 and 200020_175744 (KHA)). Funding was also obtained from the Ministerio de Ciencia e Innovación PID2019-104545RB-I00 and H2020-MSCA-ITN-2019 860070 TUBINTRAIN (JFD).Peer reviewe