Abstract: | The stereoselective synthesis of anti isomers of γ‐boryl‐substituted homoallylic alcohols is disclosed. (E)‐1,2‐Di(boryl)alk‐1‐enes undergo Ru‐catalyzed double‐bond transposition with control of the geometry. The in situ generated (E)‐1,2‐di(boryl)alk‐2‐enes add to aldehydes in a stereospecific manner. The alkenylboron group within the product is amenable to a variety of synthetic derivatizations. |