Abstract Treatment of suitably protected serine and threonine derivatives with N,N‐diethylaminodibenzylphosphoramidite, followed by subsequent treatment with tert‐butyl hydroperoxide affords the phosphorylated amino acids in good yields. After deprotection and coupling with the hydroxybenzotriazole ester from Boc‐Ala the protected phosphopeptides are obtained in good yields.