Thioesters are synthetically versatile building blocks that can be transformed to aldehydes, ketones, amides, and other functional groups under mild reaction conditions.[1] The use of malonic acid half-thioesters (MAHTs) as thioester enolate equivalents is an attractive method to mimic the biosynthesis of fatty acids and polyketides.[2–5] A highly enantioselective catalytic asymmetric decarboxylative aldol reaction of MAHT using a Cu/ ...