Beilstein J. Org. Chem.2019,15, 1545–1551, doi:10.3762/bjoc.15.157
Aromatic prenyltransferases (PTases) are enzymes that catalyze Friedel–Crafts reactions between aromatic compounds and isoprenoid diphosphates. In hapalindole biosynthesis, the aromatic PTases AmbP1 and AmbP3 exhibit surprisingly plastic selectivities. AmbP1 not only transfers the geranyl group on the C-3
of cis-indolylvinyl isonitrile, but also on the C-2, which is supressed in the presence of Mg2+ ions. AmbP3 transfers the dimethylallyl group on C-2 of hapalindole U in the reverse manner, but on C-2 of its C-10 stereoisomer in the normal manner. This review highlights the molecular bases of the
AmbP1 and AmbP3 functions, elucidated through their X-ray crystal structures. The knowledge presented here will contribute to the understanding of aromatic PTase reactions and will enhance their uses as biocatalysts.
Keywords: crystal structure; cyanobacteria; Friedel–Crafts reaction; hapalindole
Beilstein J. Org. Chem.2017,13, 1168–1173, doi:10.3762/bjoc.13.115
-52-3 has an enhanced substrate specificity towards 12-epi-hapalindole C (1) in comparison to WelO5 in H. welwitschii UTEX B1830. This allowed us to define the origin of the varied chlorinated versus dechlorinated alkaloid structural diversity between the two welwitindolinone producers. Furthermore
], analogous oxidative functionalizations with halogens via C–H activations remain challenging that need to be addressed [9][10][11]. Recently, during the systematic investigation of hapalindole-type alkaloid biogenesis [12][13][14][15][16][17][18][19], we discovered a family of Fe/2OG-dependent halogenases
molecules.
Although the initially characterized WelO5 has a restricted substrate scope [17], we have recently shown its homolog, AmbO5, in the biogenesis of ambiguines is capable of modifying seven structurally distinct hapalindole-type alkaloids [18]. The biochemical characterizations of WelO5/AmbO5
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Graphical Abstract
Figure 1:
Comparative analysis of hapalindole-type alkaloids and their BGCs in two welwitindolinone producers...