Abstract:
Numerous indole alkaloids such as the iboga- and aspidosperma-type are believed to be biosynthesized via a common hypothetical intermediate, dehydrosecodine. The highly reactive nature of dehydrosecodine-type compounds has hampered their isolation and structural elucidation. In this study, we achieved the first X-ray structural determination of a dehydrosecodine-type compound by integrating synthetic optimization of the reactivity and stabilizing the fragile molecule by encapsulation into a supramolecular host. Formation of a 1 : 1 complex of the dehydrosecodine-type labile guest bearing both vinyl indole and dihydropyridine units with the host was observed. This integrated approach not only provides insights into the biosynthetic conversions but also allows stabilization and storage of the reactive and otherwise short-lived intermediate within the confined hydrophobic cavity.
摘要:
许多吲哚生物碱,如ipoga和aspidosperma型被认为是通过一个共同的假设中间体生物合成的,脱氢西科定.脱氢塞科定型化合物的高度反应性阻碍了它们的分离和结构阐明。在这项研究中,我们通过整合反应性的合成优化和通过封装到超分子主体中来稳定脆性分子,实现了脱氢科罗定型化合物的首次X射线结构测定。观察到脱氢secodine型不稳定客体的1:1配合物与主体形成,该配合物同时带有乙烯基吲哚和二氢吡啶单元。这种整合的方法不仅提供了对生物合成转化的见解,而且还允许反应性和否则短寿命的中间体在受限的疏水腔内的稳定和储存。