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In the biosynthesis of polyketides and fatty acids, nature manipulates the enzymatic activation of malonic acid half thioesters (MAHTs) to generate thioester enolates, which undergo a chain elongation step by a decarboxylative Claisen condensation. Inspired by the biocatalytic process, scientists have attempted to mimic nature’s approach of decarboxylative organic reactions using bench-stable MAHTs as the efficient C2-unit nucleophiles and discovered diverse catalytic asymmetric processes using transitionmetal catalysts as well as organocatalysts.1 Owing to the highly versatile nature of the thioester moiety, the resulting products can be smoothly converted into a variety of useful functional groups such as alcohol, amide, aldehyde, ketone, ester, carboxylic acid derivatives, and cross-coupled products.2 The general synthetic strategy for MAHTs is shown in Scheme 1.3

Malonic Acid Half Thioesters (MAHTs) as Efficient Enolate ­Precursors in Biomimetic Catalysis

Malonic Acid Half Thioesters (MAHTs) as Efficient Enolate Precursors in Biomimetic Catalysis