TY - DATA T1 - De Novo Asymmetric Synthesis of Milbemycin β3 via an Iterative Asymmetric Hydration Approach PY - 2006/08/31 AU - Miaosheng Li AU - George A. O'Doherty UR - https://acs.figshare.com/articles/journal_contribution/De_Novo_Asymmetric_Synthesis_of_Milbemycin_sub_3_sub_via_an_Iterative_Asymmetric_Hydration_Approach/3062362 DO - 10.1021/ol061439k.s001 L4 - https://ndownloader.figshare.com/files/4768135 KW - product milbemycin β3 KW - achiral dienoate KW - Milbemycin β3 KW - 22 steps KW - milbemycin β3 KW - De Novo Asymmetric Synthesis KW - spiroketal ring system KW - Iterative Asymmetric Hydration ApproachThe enantioselective synthesis N2 - The enantioselective synthesis of the spiroketal/macrolide natural product milbemycin β3 has been achieved in 22 steps and 2.8% overall yield from an achiral dienoate. The spiroketal ring system was installed by three sequential asymmetric hydrations followed by sprioketalization. Both the absolute and relative stereochemistry of milbemycin β3 was introduced by two Sharpless asymmetric dihydroxylations, two π-allylpalladium-catalyzed reductions, and an iridium-catalyzed hydrogen migration/Claisen rearrangement to install the C-12 stereocenter. ER -