Importantly, the excellent catalytic activity, enantioselectivity, and chemoselectivity of ACCOCHF allowed this biocatalytic C-H fluorination to be easily carried out on a gram-scale with a relatively small amount of whole-cell biocatalysts, demonstrating the practicality of this biotransformation. The absolute stereochemistry of 2a was ascertained by single crystal X-ray diffraction analysis (see the SI for details).