α-Oxygenated Crotyltitanium and Dyotropic Rearrangement in the Total Synthesis of Discodermolide

A complete strategy: The total synthesis of discodermolide relies on the elaboration of syn–anti stereotriads linked to a Z‐O‐enecarbamate group, its direct transformation into the terminal Z diene, and stereocontrolled generation of the trisubstituted Z double bond by a dyotropic rearrangement (see scheme; OCb=N,N‐diisopropylcarbamoyloxy). The synthesis was achieved in 21 steps with 1.6 % overall yield.