Structures of atom replaced crypto-actACP 8a, 8b, and 8c. Access to 8a, 8b, and 8c was achieved by chemoenzymatic
conversion of mimetics 30, 31, and 32, respectively, to their corresponding CoA analogs by the
action three E. coli enzymes CoaA,
CoaD, CoaE,10 followed by loading on the
actACP by Sfp (see Supporting Information).11 Mimetic 30 contains
N and S atom replacement (blue bars) and bears structural truncation
(black-outlined bars). In mimetics 31 and 32, 1,3-dicarbonyl units are replaced by isoxazole (red bars). Two
different length substrates were examined. Shaded gray bars denote
ketide units.