Asymmetric Allylation of Glycidols Mediated by Allyl Acetate via Iridium-Catalyzed Hydrogen Transfer.

Glycidols prepared via Sharpless asymmetric epoxidation participate in asymmetric redox-neutral carbonyl allylation with good levels of catalyst-directed diastereoselectivity. Equally stereoselective allylations may be performed from the aldehyde oxidation level using 2-propanol as the terminal reductant. An epoxide ring-opening reaction using AlMe3 -n-BuLi is used to prepare the propionate-based stereotetrad spanning C17-C23 of dictyostatin, illustrating how this method may be applied to polyketide construction.