The mechanism in the asymmetrically selective oxidation of 3.4-dihydroxyphenylalanine catalyzed by the poly-L-lysine-copper(II) complex

In the oxidation of 3.4-dihydroxyphenylalanine (DOPA) the effect of the asymmetrical structure in poly-L -lysine-copper(II) complex (PLL-Cu(II)) on the asymmetrical selectivity ratio was investigated at various reaction temperatures and various preparation conditions of the catalyst, or by addition of catechol or phenylalanine. From the comparison of the asymmetric selectivity with the structure of the catalyst, the combination of two or more asymmetric cupric complex units was considered as the cause for the asymmetrically selective catalysis, where α-helical structure may serve to hold the two or more cupric complex units in a special steric configuration. Moreover a plausible mechanism for the asymmetrically selective oxidation was discussed by the evidence from the addition effects of catechol or phenylalanine and by the asymmetrically selective interaction between PLL-Cu(II) and DOPA. Then, the mechanism seems to be confirmed by an inspection with a molecular model.