Acyl-oxyallenes as α,β-unsaturated ketone surrogates for Giese radical addition.

ABSTRACT: Oxyallenes are valuable building blocks in organic synthesis, most commonly exploited as π-allyl metal precursors in transition-metal-catalyzed allylation reactions. In contrast, their engagement in radical processes remains largely unexplored. Herein, we disclose a Giese-type radical addition protocol in which acyl-substituted oxyallenes function as in situ precursors to α,β-unsaturated ketones, enabling efficient coupling with 2-azaallyl radicals. This metal-free method delivers a wide range of γ-amino ketones in high yields with broad functional group tolerance, mild conditions, and scalability to gram quantities. Mechanistic studies, including radical trapping and isotopic labeling, support a pathway involving radical addition of the 2-azaallyl radical to transient enone interme

SUBMITTER: Jin J 

PROVIDER: S-EPMC12679491 | biostudies-literature | 2026 Jan

REPOSITORIES: biostudies-literature