Hydrolase–like catalysis and structural resolution of natural products by a metal–organic framework

The exact chemical structure of non–crystallising natural products is still one of the main challenges in Natural Sciences. Despite tremendous advances in total synthesis, the absolute structural determination of a myriad of natural products with very sensitive chemical functionalities remains undone. Here, we show that a metal–organic framework (MOF) with alcohol–containing arms and adsorbed water, enables selective hydrolysis of glycosyl bonds, supramolecular order with the so–formed chiral fragments and absolute determination of the organic structure by single–crystal X–ray crystallography in a single operation. This combined strategy based on a biomimetic, cheap, robust and multigram available solid catalyst opens the door to determine the absolute configuration of ketal compounds regardless degradation sensitiveness, and also to design extremely–mild metal–free solid–catalysed processes without formal acid protons.