Stereoselective construction of skipped polyol enabled by oxonia-Cope rearrangement and iodolactonization: enantioselective synthesis of (+)-yashabushitriol

Skipped polyol is a common motif in numerous biologically significant polyketides and has been the focus of the development of novel synthetic methods and strategies. In this work, we devised a highly diastereoselective approach to access skipped triol (anti, syn-isomer) from a chiral alpha-allenic alcohol which was derived from kinetic resolution in our previous studies. An iodolactonization and subsequent radical deiodonation efficiently introduced the hydroxyl group at C3 in a highly diastereoselective manner and exemplified in enantioselective total synthesis of (+)-yashabushitriol.