Tyrosine-derived metabolites have offered much interest for their unique structures and a variety of physiologycal activities. In connection with our synthetic studies on physiologically active natural products carrying isodi-tyrosine units, total synthesis of OF4949-III (1), and K-13 (2), along with synthetic study on vancomycin (3) have been achieved. Based on the phenolic oxidation using TTN followed by zinc reduction, an aminopeptidase B inhibitor (OF4949-III, 1) and an inhibitor of angiotensin-I converting enzyme (K-13, 2) have been successfully synthesized from the corresponding tripeptides. Interesting activities against gram positive bacteria and concepts of molecular recognition have evoked total synthesis of vancomycin. Devise to construct the isotyrosine units in this antibiotic would be discussed.