Acetoacetyl-CoA reductase PhaB as an excellent anti-Prelog biocatalyst for the synthesis of chiral β-hydroxyl ester and the molecular basis of its catalytic performance

•PhaB was an excellent tool for the preparation of anti-Prelog β-hydroxyl esters.•Halogen bond was a main force of PhaB specificity toward chlorinated β-ketoesters.•Distribution of enzyme-substrate interactions was connected to enzyme activity.•Configurations of substrate and active pocket determined enzyme stereoselectivity.