Copper-Catalyzed Enantioselective Synthesis of Chiral Selenium-Based Versatile Synthons.

Enantioenriched organoselenium compounds have found diverse applications across organic synthesis, asymmetric catalysis, and medicinal chemistry, driving a growing demand for efficient catalytic approaches to access novel chiral organoselenium molecules. However, in contrast to their oxygen- and sulfur-based counterparts, catalytic asymmetric routes to selenium-based chiral compounds remain underdeveloped, and no catalytic method has been reported for preparing chiral selenium-based molecules capable of serving multiple functional roles. Here, we describe a mild and simple Cu-(II)/diamine catalytic system that delivers chiral selenium-based versatile synthons with broad downstream utility, including applications as valuable synthetic intermediates, chiral organocatalysts, and bioactive agents. Computational studies explored the possibility of enantioselectivity-determining factors and a selenium-coordinating tetradentate copper catalyst model. A broad substrate scope was performed that supported this mechanistic proposal. We anticipate that this work will furnish a robust selenium-based synthetic toolbox and expand the accessible chemical space in chiral organoselenium chemistry.