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

• Published in: Angewandte Chemie International Edition Vol. 61; no. 46
• Main Authors: Wang, Qiang, Nilsson, Tomas, Eriksson, Lars, Szabó, Kálmán J.
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 14-11-2022; John Wiley and Sons Inc
• Edition: International ed. in English
• Subjects: A-stable; Asymmetric Synthesis; Boron; Diastereoselectivities; Fluorine; Functionalized; Lewis Base; Ring opening; Selectivity; Selenium; Site selectivity; Sulfur; Synthesis; Synthetic aperture radar; Synthetic approach; Trifluoromethyl
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202210509

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.
Densely functionalized chiral allyl species, with an alkenyl CF3 group, were prepared with excellent selectivity by selenium‐catalyzed sulfenofunctionalization of allylboronic acids. The method can be used to access chiral allyl SCF3, SCF2R, SCN and SAr compounds.