Electrophilic Selenium-Catalyzed Desymmetrizing Cyclization to Access P-Stereogenic Heterocycles

The construction of phosphorus stereocenters under metal-free conditions remains a formidable challenge. Herein, we report a mechanistically distinct chiral electrophilic selenium catalysis-enabled desymmetrizing cyclization to access valuable chiral phosphorus-stereogenic heterocycles with high efficiency. This ambient temperature method affords a broad range of chiral phosphorus compounds that bear a phenolic hydroxyl group as a useful synthetic handle and, thus, enriches the toolbox for rapid generation of molecular complexity. The control experiments and DFT calculations indicate that the dual-hydrogen-bonding bridge formed between the substrate and TfO- anion plays a crucial role in determining the enantioselectivity of the transformation.