Copper‐Catalyzed Asymmetric Acylboration of 1,3‐Butadienylboronate with Acyl Fluorides

Abstract

AbstractWe report herein a Cu‐catalyzed regio‐, diastereo‐ and enantioselective acylboration of 1,3‐butadienylboronate with acyl fluorides. Under the developed conditions, the reactions provide (Z)‐β,γ‐unsaturated ketones bearing an α‐tertiary stereocenter with high Z‐selectivity and excellent enantioselectivities. While direct access to highly enantioenriched E‐isomers was not successful, we showed that such molecules can be synthesized with excellent E‐selectivity and optical purities via Pd‐catalyzed alkene isomerization from the corresponding Z‐isomers. The orthogonal chemical reactivities of the functional groups embedded in the ketone products allow for diverse chemoselective transformations, which provides a valuable platform for further derivatization.