Department of Pharmaceutical Sciences, Oregon State University, Corvallis, OR 97331, USA.
Bioorg Med Chem. 2011 Nov 15;19(22):6675-701. doi: 10.1016/j.bmc.2011.06.011. Epub 2011 Jun 12.
The structural assignment of new natural product molecules supports research in a multitude of disciplines that may lead to new therapeutic agents and or new understanding of disease biology. However, reports of numerous structural revisions, even of recently elucidated natural products, inspired the present survey of techniques used in structural misassignments and subsequent revisions in the context of constitutional or configurational errors. Given the comparatively recent development of marine natural products chemistry, coincident with modern spectroscopy, it is of interest to consider the relative roles of spectroscopy and chemical synthesis in the structure elucidation and revision of those marine natural products that were initially misassigned. Thus, a tabulated review of all marine natural product structural revisions from 2005 to 2010 is organized according to structural motif revised. Misassignments of constitution are more frequent than perhaps anticipated by reliance on HMBC and other advanced NMR experiments, especially when considering the full complement of all natural products. However, these techniques also feature prominently in structural revisions, specifically of marine natural products. Nevertheless, as is the case for revision of relative and absolute configuration, total synthesis is a proven partner for marine, as well as terrestrial, natural products structure elucidation. It also becomes apparent that considerable 'detective work' remains in structure elucidation, in spite of the spectacular advances in spectroscopic techniques.
新天然产物分子的结构分配支持了许多学科的研究，这些研究可能导致新的治疗剂或对疾病生物学的新理解。然而，大量结构修订报告，甚至是最近阐明的天然产物，激发了本调查，以了解在结构错误和随后的修订中出现的构象或构型错误的技术。鉴于海洋天然产物化学与现代光谱学的相对较近的发展，考虑到在最初被错误分配的海洋天然产物的结构阐明和修订中光谱学和化学合成的相对作用是很有趣的。因此，根据修订的结构模体，按照结构主题对 2005 年至 2010 年所有海洋天然产物结构修订的表格综述进行了组织。仅依靠 HMBC 和其他高级 NMR 实验，对构象的错误分配可能比预期的更为频繁，尤其是考虑到所有天然产物的全部成分时。然而，这些技术在结构修订中也占有突出地位，特别是对海洋天然产物的结构修订。尽管光谱技术取得了惊人的进步，但对于相对和绝对构型的修订来说，全合成是海洋以及陆地天然产物结构阐明的可靠方法。即使在光谱技术取得了惊人的进步的情况下，结构阐明仍有大量“侦探工作”需要完成，这一点也变得很明显。
