2.5.1.34 dimethylallyl diphosphate + L-tryptophan = diphosphate + 4-(3-methylbut-2-enyl)-L-tryptophan - - 2.5.1.34 dimethylallyl diphosphate + L-tryptophan = diphosphate + 4-(3-methylbut-2-enyl)-L-tryptophan ability of dimethylallyltryptophan synthase to prenylate at five different sites on the indole nucleus, with normal and reverse prenylation at one of the sites, is consistent with a dissociative electrophilic alkylation of the indole ring, where orientation of the substrates within the active site and substituent electronic effects determine the position and type of prenylation 722461 2.5.1.34 dimethylallyl diphosphate + L-tryptophan = diphosphate + 4-(3-methylbut-2-enyl)-L-tryptophan catalytic reaction mechanism, overview 722461 2.5.1.34 dimethylallyl diphosphate + L-tryptophan = diphosphate + 4-(3-methylbut-2-enyl)-L-tryptophan Cope mechanism for the reaction catalyzed by DMAT synthase, overview 722452 2.5.1.34 dimethylallyl diphosphate + L-tryptophan = diphosphate + 4-(3-methylbut-2-enyl)-L-tryptophan enzyme-catalyzed sigmatropic process in the C-4 prenylation of indole alkaloids, an initial reverse prenylation of tryptophan at C-3 with dimethylallyl diphosphate, the subsequent Cope rearrangement shifts the prenyl moiety to the C-4 position and re-aromatization gives dimethylallyltryptophan, reaction mechanism,overview 721293 2.5.1.34 dimethylallyl diphosphate + L-tryptophan = diphosphate + 4-(3-methylbut-2-enyl)-L-tryptophan random sequential mechanism -, 637463 2.5.1.34 dimethylallyl diphosphate + L-tryptophan = diphosphate + 4-(3-methylbut-2-enyl)-L-tryptophan reaction mechanism and substrate specificity, overview 723326 2.5.1.34 dimethylallyl diphosphate + L-tryptophan = diphosphate + 4-(3-methylbut-2-enyl)-L-tryptophan sequential mechanism -, 637459 2.5.1.34 dimethylallyl diphosphate + L-tryptophan = diphosphate + 4-(3-methylbut-2-enyl)-L-tryptophan SN1-like mechanism involving a discrete carbocation intermediate involving initial ion pair formation followed by a reverse prenylation at the nucleophilic C-3 position, detailed overview 726466 2.5.1.34 dimethylallyl diphosphate + L-tryptophan = diphosphate + 4-(3-methylbut-2-enyl)-L-tryptophan stereochemistry, direct attack of dimethylallyl diphosphate on C-4 of the indole 637460 2.5.1.34 dimethylallyl diphosphate + L-tryptophan = diphosphate + 4-(3-methylbut-2-enyl)-L-tryptophan studies are presented that strongly support the dissociative mechanism for the DMAT synthase reaction. The observation of positional isotope exchange (PIX) in isotopically labeled DMAPP provides evidence for the existence of a dimethylallyl carbocation intermediate 704180 2.5.1.34 dimethylallyl diphosphate + L-tryptophan = diphosphate + 4-(3-methylbut-2-enyl)-L-tryptophan the mechanism of this enzyme-catalyzed Friedel–Crafts reaction represents strict regioselectivity at the C4 position of the indole ring of L-tryptophan, proposed reaction mechanism for Aspergillus fummigatus FgaPT2 involving Glu89 and Lys174 737837