Philipps-Universität Marburg, Institut für Pharmazeutische Biologie und Biotechnologie, Deutschhausstrasse 17A, D-35037 Marburg, Germany.
Org Biomol Chem. 2012 Dec 14;10(46):9262-70. doi: 10.1039/c2ob26149a. Epub 2012 Oct 23.
The prenyltransferase FtmPT1 from Aspergillus fumigatus is involved in the biosynthesis of fumitremorgin-type alkaloids and catalysed the regular C2-prenylation of brevianamide F (cyclo-L-Trp-L-Pro). It has been shown that FtmPT1 also accepted a number of other tryptophan-containing cyclic dipeptides and prenylated them, in the presence of dimethylallyl diphosphate, at C-2 of the indole nucleus. Detailed analysis of the incubation mixtures of FtmPT1 with these cyclic dipeptides revealed the presence of additional product peaks in the HPLC chromatograms. Seven regularly C3-prenylated hexahydropyrrolo[2,3-b]indoles were isolated and identified by HR-ESI-MS and NMR analyses including HMBC, HMQC and NOESY experiments. Further experiments proved that the C2- and C3-prenylated products are both independent enzyme products. To the best of our knowledge, this is the first report on the enzymatic formation of regularly C3-prenylated indolines. A reaction mechanism for both C2- and C3-prenylated derivatives was proposed.
来自烟曲霉的烯基转移酶 FtmPT1 参与了 fumitremorgin 型生物碱的生物合成，并催化了 brevianamide F（环-L-色氨酸-L-脯氨酸）的规则 C2-烯丙基化。已经表明，FtmPT1 还接受了许多其他含色氨酸的环状二肽，并在二甲基烯丙基二磷酸的存在下，在吲哚核的 C-2 处对其进行烯丙基化。对 FtmPT1 与这些环状二肽的孵育混合物的详细分析显示，在 HPLC 色谱图中存在其他产物峰。通过 HR-ESI-MS 和 NMR 分析（包括 HMBC、HMQC 和 NOESY 实验）分离并鉴定了 7 种规则 C3-烯丙基化的六氢吡咯并[2,3-b]吲哚。进一步的实验证明，C2-和 C3-烯丙基化产物都是独立的酶产物。据我们所知，这是关于规则 C3-烯丙基化吲哚的酶促形成的第一个报告。提出了 C2-和 C3-烯丙基化衍生物的反应机制。
