Enantioselective Vinylogous Addition of Enones to Allenes Enabled by Synergistic Borane/Palladium Catalysis

J Am Chem Soc. 2025 Jan 8;147(1):104-110. doi: 10.1021/jacs.4c16214. Epub 2024 Dec 24.

Abstract

Herein, we report a method for enantioselective vinylogous addition of enones to alkoxyallenes enabled by synergistic borane/palladium catalysis. The inductive effect provided by borane coordination to the ketone was essential for closing the gap between the conditions needed for the generation of a dienolate and those needed for initiation of the palladium catalytic cycle by protonation of the metal catalyst. Furthermore, we accomplished the first example of stereodivergent synthesis with chiral borane/transition-metal catalysts.