A Novel Strategy for the Convergent Synthesis of 1,3,5,…-Polyols: Enone Formation, Asymmetric Dihydroxylation, Reductive Cleavage, Hydride Addition

Abstract Asymmetric dihydroxylation of α,β-unsaturated ketones provided α,β-dihydroxyketones with up to 100% ee. The C α -O bond of these intermediates or their bis-TMS ethers, acetonides, phenylborates or orthoformiates was cleaved with SmI 2 , affording β-hydroxyketones. The latter can be reduced to furnish SYN- or ANTI-configured 1,3-diols of any desired configuration.