Regio- and enantioselective synthesis of (S)-(+)-3-arylamino-1-chloropropan-2-ols has been achieved by epoxide ring opening of (±)-epichlorohydrin with different aromatic amines in the presence of Candida rugosa lipase. Activity of seven model (S)-(+)-3-arylamino-1-chloropropan-2-ols, out of 10 compounds synthesized, has been evaluated for the inhibition of tumor necrosis factor-α (TNF-α) induced expression of cell adhesion molecule, that is, intercellular adhesion molecule-1 (ICAM-1) and structure–activity relationship has been established. Graphical abstract for this article