Stereoselective Construction of β-chiral Homoallyl Functionalities by Substrate- and Reagent-Controlled Iterative 1,2-Metallate Rearrangements

[Image: see text] Homoallylic alcohols possessing chiral β-centers are considered highly valuable in the synthesis of polyketide-based natural products. Therefore, there is a significant demand for new methods that allow for their stereoselective access. In pursuit of this objective, we have successfully combined our substrate-controlled protocol of Hoppe–Matteson–Aggarwal chemistry with iterative 1,2-metallate rearrangements. Notably, this approach has proven effective in introducing not only primary alcohols but also other functional groups such as alkynes and protected amines.