To further demonstrate the synthetic utility of our newly developed photometallobiocatalytic enantioconvergent azidation and thiocyanation, we carried out preparative scale enzymatic synthesis and performed downstream transformations to convert organic azide and thiocyanate building blocks into synthetically useful products. Using commercially available Kessil blue LED lamps, the photobiocatalytic azide product (R)-3a was isolated in 58% yield with 99.5:0.5 e.r.. Starting from (R)-3a, phosphoramidate 9 and primary amine 11 were obtained in excellent yield and enantiomeric retention via the Staudinger reaction. Additionally, a click reaction with an aryl alkyne afforded the triazole 10 in 83% yield with 99:1 e.r., demonstrating the versatility of the chiral azide compounds 39 Meanwhile, using (rac)-1a, the thiocyanate product (R)-5a was generated in 46% yield and 95:5 e.r.. Furthermore, SCF3 40 derivatives 12 and S-tetrazole 41 13 was obtained in good yield, highlighting the potential for incorporating other functionalities. Scheme 3. Derivatization of Enantioenriched Secondary Alkyl Azides and Thiocyanates