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The amino acids’ side chains act as the relay device to modulate the chemical reactivity of the N-phosphoryl amino acids. The N-dialkyl phosphoryl cysteine is stable, but the N-dialkyl phosphoryl serine or threoine was converted into many kinds of products at 40℃. The N-dialkyl phosphoryl gltamic acid is a stable compound, while the N-dislkyl phosphoryl aspartic acid was transferred into the peptides, esters and the phosphoryl ester-exchanged products under mild conditions. The N-dialkyl phosphoryl histidine has the similar reactivity through the co-participation of the side chain, carboxyl and phosphoryl groups. A hexacoordinate phosphorus was proposed to account for this differentiation and promotion effect.