Enantioselective Desymmetrization of Diynes

In the field of asymmetric synthesis, the desymmetrization of prochiral diynes has arisen as a challenging yet effective strategy for the rapid and efficient construction of structurally diverse and complex molecules. This review explores the various methodologies (cycloadditions, cycloisomerizations, and C‐ and X‐ additions) that enable the enantiotopic discrimination within various symmetric diyne systems, resulting in the generation of central (both carbon and heteroatom), planar, and axial chirality.