Tyrosine O-Prenyltransferases TyrPT and SirD displaying similar behavior unnatural or benzyl disphosphate as their natural prenyl donor dimethyallyl diphosphate


Prenyltransferases of the dimethylallyltryptophan synthase (DMATS) superfamily are involved in the biosynthesis of secondary metabolites and contribute as modification enzymes significantly to structural diversity of natural products. They show usually broad specificity toward their aromatic substrates with regiospecific prenylations on aromatic rings. However, most members of this superfamily exhibit a high specificity toward their prenyl donors and usually accept exclusively dimethylallyl diphosphate (DMAPP). Recently, several indole prenyltransferases from this family were also demonstrated to accept unnatural DMAPP analogs such as methylallyl, 2-pentenyl and benzyl diphosphate for alkylation, or benzylation of the indole ring. Partial or complete shift of the substitution position was observed for these enzymes. In this study, we report the acceptance of these DMAPP analogs by two tyrosine O-prenyltransferases TyrPT from Aspergillus niger and SirD from Leptosphaeria maculans for alkylation or benzylation of tyrosine and derivatives. NMR and mass spectrometry (MS) analyses of nine isolated enzyme products confirmed the regiospecific O- or N-alkylation or benzylation at position C-4 of the aromatic ring, which is the same prenylation position of these enzymes in the presence of DMAPP.


Huili Yu, Mike Liebhold, Xiulan Xie, Shu-Ming Li


Applied Microbiology and Biotechnology

Year, Volume, Page

2015, 99, 7115



Tag Element Regiochemistry Product Substrate Cofactor Enzyme
PTDBREC00562 O Regular TyrPT
PTDBREC00563 N Regular SirD
PTDBREC00564 O Regular SirD
PTDBREC00565 O Regular TyrPT
PTDBREC00566 O Regular SirD
PTDBREC00567 O Regular TyrPT
PTDBREC00568 O Regular SirD
PTDBREC00569 O Regular TyrPT
PTDBREC00570 O Regular SirD
PTDBREC00571 O Regular TyrPT
PTDBREC00572 O Regular SirD
PTDBREC00573 O Regular TyrPT
PTDBREC00574 O Regular SirD
PTDBREC00575 N Regular TyrPT
PTDBREC00576 N Regular SirD
PTDBREC00577 O Regular TyrPT
PTDBREC00578 O Regular SirD
PTDBREC00579 O Regular SirD
PTDBREC00580 O Regular TyrPT
PTDBREC00581 O Regular SirD
PTDBREC00582 O Regular TyrPT
PTDBREC00583 O Regular SirD
PTDBREC00584 O Regular TyrPT
PTDBREC00585 O Regular SirD
PTDBREC00586 O Regular TyrPT
PTDBREC00587 O Regular SirD
PTDBREC00588 O Regular TyrPT
PTDBREC00589 N Regular TyrPT
PTDBREC00590 O Regular SirD
PTDBREC00591 O Regular TyrPT
PTDBREC00592 O Regular SirD
PTDBREC00593 O Regular TyrPT
PTDBREC00594 O Regular SirD
PTDBREC00595 O Regular TyrPT
PTDBREC00596 O Regular SirD
PTDBREC00597 O Regular TyrPT
PTDBREC00598 O Regular SirD
PTDBREC00599 O Regular TyrPT
PTDBREC00600 N Regular SirD
PTDBREC00601 O Regular SirD
PTDBREC00602 O Regular TyrPT
PTDBREC00603 O Regular SirD
PTDBREC00604 O Regular TyrPT
PTDBREC00605 O Regular SirD
PTDBREC00606 O Regular TyrPT
PTDBREC00607 O Regular SirD
PTDBREC00608 O Regular TyrPT
PTDBREC00609 O Regular SirD
PTDBREC00610 O Regular TyrPT
PTDBREC00611 O Regular TyrPT
PTDBREC00612 O Regular SirD
PTDBREC00613 O Regular TyrPT
PTDBREC00614 O Regular SirD
PTDBREC00615 O Regular TyrPT
PTDBREC00616 O Regular SirD
PTDBREC00617 O Regular TyrPT
PTDBREC00618 O Regular SirD
PTDBREC00619 O Regular TyrPT
PTDBREC00620 O Regular SirD
PTDBREC00621 O Regular TyrPT
PTDBREC00622 O Regular SirD
PTDBREC00623 O Regular SirD
PTDBREC00624 O Regular TyrPT
PTDBREC00625 O Regular SirD
PTDBREC00626 O Regular TyrPT
PTDBREC00627 O Regular SirD
PTDBREC00628 O Regular TyrPT
PTDBREC00629 O Regular SirD
PTDBREC00630 O Regular TyrPT
PTDBREC00631 O Regular SirD
PTDBREC00632 O Regular TyrPT
PTDBREC00633 O Regular TyrPT
PTDBREC00634 O Regular SirD
PTDBREC00635 O Regular TyrPT
PTDBREC00636 O Regular SirD
PTDBREC00637 O Regular TyrPT
PTDBREC00638 O Regular SirD
PTDBREC00639 O Regular TyrPT
PTDBREC00640 O Regular SirD
PTDBREC00641 O Regular TyrPT
PTDBREC00642 O Regular SirD
PTDBREC00643 O Regular TyrPT
PTDBREC00644 O Regular SirD
PTDBREC00645 O Regular SirD
PTDBREC00646 N Regular TyrPT
PTDBREC00647 N Regular SirD
PTDBREC00648 O Regular TyrPT
PTDBREC00649 O Regular SirD
PTDBREC00650 O Regular TyrPT
PTDBREC00651 O Regular SirD
PTDBREC00652 O Regular TyrPT
PTDBREC00653 O Regular SirD
PTDBREC00654 O Regular TyrPT
PTDBREC00655 N Regular TyrPT
PTDBREC00656 O Regular SirD
PTDBREC00657 O Regular TyrPT
PTDBREC00658 O Regular SirD
PTDBREC00659 O Regular TyrPT
PTDBREC00660 O Regular SirD
PTDBREC00661 O Regular TyrPT