Supramolecular catalysis hydroformylation

Supramolecular chemistry has been a very popular research topic for three decades now. Most applications are foreseen in sensors and opto-electronical devices. Supramolecular catalysis often refers to the combination of a catalyst with a synthetic receptor molecule that preorganizes the substrate-catalyst complex and has also been proposed as an important possible application. The concept, which has proven to be powerful in enzymes, has mainly been demonstrated by chemists that investigated hydrolysis reactions. Zinc and copper in combination with cyclodextrins as the receptor dramatically enhance the rate ofhydrolysis. So far, the ample research devoted to transition metal catalysis has not been extended to supramolecular transition metal catalysis. A rare example of such a supramolecular transition metal catalyst was the results of the joined efforts of the groups of Nolte and Van Leeuwen [SO], They reported a basket-shaped molecule functionalized with a catalytically active rhodium complex that catalyzed hydrogenation reactions according to the principles of enzymes. The system showed substrate selectivity, Michaelis Menten kinetics and rate enhancement by cooperative binding of substrate molecules. The hydroformylation of allyl catachol substrates resulted in a complex mixture of products. 

After Breit and Seiche (67) had reported hydroformylation catalysts containing rhodium and bidentate ligands assembled via hydrogen bonding, Dubrovina and Boerner (68) pointed out that the first use of bidentate ligands obtained via hydrogen bonding in catalysis is represented by the supramolecular work on SPO platinum complexes. 

The supramolecular binding motifs described here were also used to attach catalysts to solid (silica) supports (128). The active metal complex could be switched from palladium to rhodium by using a polar solvent that breaks up the binding of the supramolecular motif. Allylic alkylation and hydroformylation catalysis could be carried out by using the same support "receptor" material and different "guest" ligands for the two metals a... 

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