Supramolecular synthesis of coumarin derivatives catalyzed by a coordination-assembled cage in aqueous solution
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摘要:
A self-assembled Pd4L2 cage is employed as a water-soluble molecular flask for the synthesis of functionalized coumarins from a series of salicylaldehyde derivatives and cyanoacetates/malononitrile.The catalytic reaction features mild aqueous conditions and broad substrate scope.Crystal structures of the host-guest complexes for two substrates and one analogous intermediate have been obtained,shedding light on the supramolecular reaction mechanism.Michaelis-Menten kinetic studies were performed in one typical case,revealing that the rate of product formation has been enhanced by over 23-fold in contrast to the background reaction without cage.Moreover,the same reaction catalyzed by a smaller Pd6L4 cage gives a mixture of products and much lower yields,suggesting that fine-tuning on the size and symmetry of the cages' cavity is crucial for their applications in supramolecular catalysis.