Bringmann G, Lang G
Institute of Organic Chemistry, University of Würzburg, Am Hubland, 97074 Würzburg, Germany.
Prog Mol Subcell Biol. 2003;37:89-116. doi: 10.1007/978-3-642-55519-0_4.
This chapter deals with an efficient methodology available in our Center of Excellence, BIOTECmarin: the novel analytical 'triad' HPLC-MS/MS-NMR-CD. By this method, which was, in this complemented form, first introduced into phytochemical research by our group, we can not only rapidly identify known structures, but can also investigate new metabolites and establish their full absolute stereostructures online, directly from crude extracts, without the necessity of first isolating the compounds. The LC-CD option, which we have been using for the first time in natural products analysis, becomes even more valuable by the possibility of interpreting the online CD spectra by their simulation or prediction through quantum chemical calculation, thus avoiding the usual, often risky, empirical comparison with the CD spectra of (sometimes not so related) compounds of known absolute stereostructure or the application of (sometimes not really applicable) likewise empirical CD rules. The hyphenated analytical methods are additionally complemented by our synthetic expertise, again involving new concepts and strategies developed in our group. The methods and their application will first be explained and exemplified for plant-derived ('terrestrial') natural products, for which they were initially developed, and will then be applied to the online structural elucidation of novel natural products from marine organisms.
本章介绍了我们卓越中心BIOTECmarin所采用的一种高效方法：新颖的分析“三联体”——高效液相色谱-串联质谱-核磁共振-圆二色光谱（HPLC-MS/MS-NMR-CD）。通过这种由我们团队首次以这种补充形式引入植物化学研究的方法，我们不仅能够快速鉴定已知结构，还能研究新的代谢产物，并直接从粗提物中在线确定它们完整的绝对立体结构，而无需先分离化合物。我们首次在天然产物分析中使用的液相色谱-圆二色光谱（LC-CD）选项，通过量子化学计算对在线圆二色光谱进行模拟或预测来解释，变得更具价值，从而避免了通常的、往往有风险的与已知绝对立体结构（有时并非密切相关）化合物的圆二色光谱进行经验性比较，也避免了应用（有时并非真正适用）同样经验性的圆二色光谱规则。联用分析方法还通过我们的合成专业知识得到补充，这同样涉及我们团队开发的新概念和策略。这些方法及其应用将首先针对最初为植物源（“陆地”）天然产物开发的情况进行解释和举例说明，然后将应用于海洋生物中新天然产物的在线结构解析。
