To demonstrate the synthetic utility of ß-fluoro-α-ketoacids as aldolase donors, selected reactions relevant to bioactive compounds were conducted on a larger scale and the products isolated (Figure , Figure ). All products were confirmed by 1 H, C, and F NMR (Figure ). Compounds 7a, 7b, and 7c derived from formaldehyde are fluorine-bearing versions of the Roche ester (methyl 3-hydroxy-2methylpropionate). This versatile building block has been employed in classic total syntheses of complex natural products, such as the anticancer discodermolide. The aromatic products 8a and 8b resemble known arylbutyryl intermediates of nikkomycins, a family of antifungal compounds also targeted for total synthesis. The above five compounds were prepared by a sequence of enzymatic reaction (0.6 mmol), decarboxylation with H2O2, removal of water and enzymes, and esterification in MeOH/HCl or EtOH/SOCl2 before extraction and chromatography. Additionally, the enantioselectivity was confirmed by derivatization with Mosher's acid and comparison with chemically synthesized racemic standards (Table , Figure , Figure ). Lastly, the α-fluoro-α-methyl branched sugar acids 5j and 5k were enzymatically synthesized (0.15 mmol) and directly purified by semi-preparative HPLC. Similar intermediates are used to synthesize the fluorinated pentose moiety of the blockbuster antiviral sofosbuvir, which could be potentially accessed by using aldolase families with opposing stereochemical preference. These examples demonstrate that the combination of aldolases with novel fluoro-donor substrates provides flexible access to fragments bearing valuable C-F stereocenters, and potentially enables new fluorinated drugs or fluorinated analogs of known drugs.