Mimicry of Polyketide Synthases—Enantioselective 1,4‐Addition Reactions of Malonic Acid Half‐Thioesters to Nitroolefins

Bifunctionality is the key for mimicking the active site of polyketide synthases with synthetic metal-free organocatalysts (see picture). Cinchona alkaloid derivatives bearing both a basic site and a urea moiety catalyze conjugate enantioselective addition reactions of malonic acid half thioesters (MAHTs) to nitroolefins with up to quantitative yields and selectivities up to 90 % ee.