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Cofactor-Controlled Chirality of Tropoisomeric Ligand

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journal contribution
posted on 23.05.2016, 13:19 by Laure Théveau, Rosalba Bellini, Paweł Dydio, Zoltan Szabo, Angela van der Werf, Robin Afshin Sander, Joost N. H. Reek, Christina Moberg
A new tropos ligand with an integrated anion receptor site has been prepared. Chiral carboxylate and phosphate anions that bind in the anion receptor unit proved capable of stabilizing chiral conformations of the achiral flexible bidentate biaryl phosphite ligand, as shown by variable temperature 1H and 31P NMR spectroscopical studies of palladium(0) olefin complexes. Palladium allyl complexes of the supramolecular ligand-chiral cofactor assemblies catalyzed asymmetric allylic substitutions of rac-(E)-1,3-diphenyl-2-propenyl carbonate and rac-3-cyclohexenyl carbonate with malonate and benzylamine as nucleophiles to provide nonracemic products. Although moderate enantioselectivities were observed, (ee:s up to 66%), the results confirm the ability of the anionic guests to affect the conformation of the ligand.