Department of Chemistry, Imperial College London, South Kensington Campus, London SW7 2AZ, UK.
Chemistry. 2011 Oct 10;17(42):11868-75. doi: 10.1002/chem.201101129. Epub 2011 Sep 5.
Isolation and semisynthetic modification of the fungal metabolite chaetocin gave access to a desulfurized analogue of this natural product. Detailed chiroptical studies, comparing experimentally obtained optical rotation values, electronic circular dichroism spectra, and vibrational circular dichroism spectra to computationally simulated ones, reveal the desulfurization of chaetocin to unambiguously proceed with retention of configuration. Consideration of the plausible mechanisms for this process highlighted inconsistencies in the stereochemical assignment of related molecules in the literature. This in turn allowed the stereochemical reassignment of the natural product analogue dethiodehydrogliotoxin.
真菌代谢产物 chaetocin 的分离和半合成修饰，得到了该天然产物的脱硫类似物。详细的手性研究，通过比较实验获得的旋光值、电子圆二色光谱和振动圆二色光谱与计算模拟的旋光值、电子圆二色光谱和振动圆二色光谱，揭示了 chaetocin 的脱硫反应是以构型保持的方式进行的。考虑到这一过程的可能机制，突出了文献中相关分子的立体化学归属存在不一致之处。这反过来又使得天然产物类似物 dethiodehydrogliotoxin 的立体化学重新归属成为可能。
