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Predicted biosynthesis pathway of the hemiketal–acetal linkage of paeoniflorin. Compounds 1 and 3 are possible intermediates; the representative of compound 2 is mudanpioside F; the representatives of compound 4 are paeonisuffrone and 1-O-D-glucopyranosyl-8-O-benzoylpaeonisuffrone; the representative of compound 5 is paeonidaninol A; the representative of compound 6 is paeoniflorin; R1 and R2 represent the possible modification groups.
