Sulfenofunctionalization of Chiral α‐Trifluoromethyl Allylboronic Acids: Asymmetric Synthesis of SCF3, SCF2R, SCN and SAr Compounds.

We report herein a new method for the synthesis of densely functionalized chiral allyl SCF3, SCF2R, SCN and SAr species with a separate CF3 functionality. The synthetic approach is based on selenium‐catalyzed sulfenofunctionalization of chiral α‐CF3 allylboronic acids. The reactions proceeded with remarkably high stereo‐, diastereo‐ and site‐selectivity, based on the formation of a stable thiiranium ion followed by rapid deborylative ring opening. [ABSTRACT FROM AUTHOR]