Allenes are important structural motifs found in numerous natural products and are frequently used as key synthetic intermediates due to their unique reactivity. A useful method to access allenes is 1,4-addition to 1,3-enynes. We sought to merge the concept of conjunctive cross-coupling with the known reactivity of 1,3-enynes to establish a new reaction manifold, in which the nucleophile would arise in the form of a boron-“ate” complex, and a transition metal would serve as the electrophile. Herein we reported a diastereoselective and enantioselective palladium catalyzed conjunctive cross-coupling reaction that allows for the synthesis of tri-substituted allenes from borylenynes. Uniquely, both axial chirality of the allene as well as central chirality are introduced simultaneously with both under the control of a chiral catalyst. During the investigation, we discovered that a special acenaphthoquinone-derived ligand on boron was necessary for high reactivity and stereoselectivity for the reaction.

Diastereoselective and enantioselective conjunctive cross-coupling of borylenynes to afford tri-substituted allenic boronic esters

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.