7-(15)N-奥罗定的合成及在吡咯并咪唑生物碱生物合成研究中的应用 通过微尺度 (1)H-(15)N HSQC 和 FTMS 的评价
Synthesis of 7-(15)N-Oroidin and evaluation of utility for biosynthetic studies of pyrrole-imidazole alkaloids by microscale (1)H-(15)N HSQC and FTMS.
机构信息
Department of Chemistry, Texas A&M University, Texas 77842-3012, USA.
出版信息
J Nat Prod. 2010 Mar 26;73(3):428-34. doi: 10.1021/np900638e.
Numerous marine-derived pyrrole-imidazole alkaloids (PIAs), ostensibly derived from the simple precursor oroidin, 1a, have been reported and have garnered intense synthetic interest due to their complex structures and in some cases biological activity; however very little is known regarding their biosynthesis. We describe a concise synthesis of 7-(15)N-oroidin (1d) from urocanic acid and a direct method for measurement of (15)N incorporation by pulse labeling and analysis by 1D (1)H-(15)N HSQC NMR and FTMS. Using a mock pulse labeling experiment, we estimate the limit of detection (LOD) for incorporation of newly biosynthesized PIA by 1D (1)H-(15)N HSQC to be 0.96 microg equivalent of (15)N-oroidin (2.4 nmole) in a background of 1500 microg of unlabeled oroidin (about 1 part per 1600). 7-(15)N-Oroidin will find utility in biosynthetic feeding experiments with live sponges to provide direct information to clarify the pathways leading to more complex pyrrole-imidazole alkaloids.
已经报道了许多海洋衍生的吡咯并咪唑生物碱（PIA），它们显然源自简单的前体或洛丁，1a，并由于其复杂的结构和在某些情况下的生物活性而引起了强烈的合成兴趣；然而，关于它们的生物合成知之甚少。我们描述了从尿刊酸合成 7-(15)N-或洛丁（1d）的简洁合成方法，以及通过脉冲标记和通过 1D(1)H-(15)N HSQC NMR 和 FTMS 分析直接测量 (15)N 掺入的方法。使用模拟脉冲标记实验，我们估计 1D(1)H-(15)N HSQC 中通过新生物合成 PIA 的掺入的检测限（LOD）为在 1500μg 未标记的或洛丁（约 1 份/1600）背景下，新生物合成的 PIA 的 1D(1)H-(15)N HSQC 的检测限为 0.96μg 当量的 (15)N-或洛丁（2.4nmole）。7-(15)N-或洛丁将在与活海绵的生物合成喂养实验中找到用途，以提供直接信息来阐明导致更复杂的吡咯并咪唑生物碱的途径。
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