Chemo‐, Regio‐ and Stereoselective Preparation of (Z)‐2‐Butene‐1,4‐Diol Monoesters via Pd‐Catalyzed Decarboxylative Acyloxylation.

(<italic>Z</italic>)‐alkenes are useful synthons but thermodynamically less stable than their (<italic>E</italic>)‐isomers and typically more difficult to prepare. The synthesis of 1,4‐hetero‐bifunctionalized (<italic>Z</italic>)‐alkenes is particularly challenging due to the inherent regio‐ and stereoselectivity issues. Herein we demonstrate a general, chemoselective and direct synthesis of (<italic>Z</italic>)‐2‐butene‐1,4‐diol monoesters. The protocol operates within a Pd‐catalyzed decarboxylative acyloxylation regime involving vinyl ethylene carbonates (VECs) and various carboxylic acids as the reaction partners under mild and operationally attractive conditions. The newly developed process allows access to a structurally diverse pool of (<italic>Z</italic>)‐2‐butene‐1,4‐diol monoesters in good yields and with excellent regio‐ and stereoselectivity. Various synthetic transformations of the obtained (<italic>Z</italic>)‐2‐butene‐1,4‐diol monoesters demonstrate how these synthons are of great use to rapidly diversify the portfolio of these formal desymmetrized (<italic>Z</italic>)‐alkenes. [ABSTRACT FROM AUTHOR]