An Unorthodox Enolate-Triggered Radical Relay Directs the Chemo Upgrading of Levulinic Acid Into Citramalic Acid.

ABSTRACT: We report a transition-metal-free and highly selective chemical transformation of levulinic acid into citramalic acid via t-butoxide-mediated enolate chemistry, complementing both the biotransformation of glucose and glycerol using E. coli as well as transition-metal-catalyzed processes based on levulinic acid. The atypical behavior of t-butoxide-classically recognized as a base that favors kinetic enolate formation in carbonyl chemistry-proves crucial for accessing the thermodynamic enolate under elevated temperatures and extended reaction times, thereby directing the reaction toward citramalic acid as the major product. Radical-trapping experiments with TEMPO (2,2,6,6-tetramethylpiperidine 1-oxyl) and benzoic acid significantly diminished the product yield, indicating the involvement of

SUBMITTER: Kim GH 

PROVIDER: S-EPMC12932077 | biostudies-literature | 2026 Feb

REPOSITORIES: biostudies-literature