•Desymmetrization of meso-diols is a useful method for natural products synthesis.•Catalytic method using enzyme, organic compound, and metal complex have been developed.•Acylation, hydrolysis, etherification, oxidation are used for desymmetrization.•Tandem type reaction including desymmetrization step have been demonstrated.The desymmetrization of meso compounds is one of the most effective strategies for asymmetric synthesis. This digest focuses on recent progress in the desymmetrization of meso-diols and their derivatives. The topics discussed here include methods for the enzymatic acylation of meso-diols and the hydrolysis of meso-diesters, acylation, related reactions of meso-diols with organocatalysts and metal catalysts, the oxidation of meso-diols by enzymes, organocatalysts, and metal catalysts, and the desymmetrization of meso-dicarbamates with metal catalysts. The desymmetrization of meso-diols using tandem reactions is also discussed.Download high-res image (88KB)Download full-size image

Tandem asymmetric hydrogen transfer oxidation/aldol condensation under relay catalysis of a chiral iridium complex/achiral Brønsted base binary system is described for the synthesis of α-benzylidene-γ-hydroxytetralones with high ee’s. A two-step synthesis of catalponol was achieved using this sequential methodology together with regio- and stereoselective hydroboration.

The catalytic oxidative desymmetrization of meso-diols was realized using a chiral iridium catalyst. In particular, the reaction is effective for the cyclic diols to give the corresponding hydroxy ketones in high chemical yields with high ee’s. With this reaction as a key step, a short-step synthesis of common intermediate of ottelione and scyphostatin was achieved.