Philipps-Universität Marburg, Institut für Pharmazeutische Biologie, Deutschhausstrasse 17A, D-35037, Marburg, Germany.
Org Biomol Chem. 2010 Mar 7;8(5):1133-41. doi: 10.1039/b922440h. Epub 2010 Jan 7.
Nine reversely C3-prenylated pyrrolo[2,3-b]indoles were successfully prepared by using two recombinant enzymes involved in the biosynthesis of acetylaszonalenin from Neosartorya fischeri. The prenyltransferase AnaPT catalysed the conversion of six tryptophan-containing cyclic dipeptides to reversely C3-prenylated indoline derivatives. Using cyclo-L-Trp-L-Trp as substrate, both mono- and diprenylated indolines were obtained. Two of the AnaPT products were acetylated at position N1 by the acetyltransferase AnaAT. The structures of the obtained compounds were characterised by HR-ESI-MS, (1)H- and (13)C-NMR analyses as well as by long-range (1)H-(13)C connectivities in heteronuclear multiple-bond correlation (HMBC) spectra after preparative isolation. Their absolute configurations were determined by analysing the (1)H-(1)H spatial correlations in rotating-frame nuclear overhauser effect spectroscopy (ROESY).
从 Neosartorya fischeri 中涉及乙酰阿佐那林生物合成的两种重组酶成功制备了 9 种反向 C3-香叶基化吡咯并[2,3-b]吲哚。烯丙基转移酶 AnaPT 催化 6 种含色氨酸的环二肽转化为反向 C3-香叶基化吲哚啉衍生物。使用环-L-Trp-L-Trp 作为底物，得到了单和二烯基化的吲哚啉。AnaPT 的两种产物在位置 N1 被乙酰基转移酶 AnaAT 乙酰化。通过 HR-ESI-MS、（1）H 和（13）C-NMR 分析以及异核多键相关（HMBC）谱中的远程（1）H-（13）C 连接性对获得的化合物进行了结构表征，在制备分离后。通过分析旋转框架核奥弗豪瑟效应光谱（ROESY）中的（1）H-（1）H 空间相关来确定它们的绝对构型。
