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Paper | Special issue | Vol 74, No. 1, 2007, pp.357-367
Published online, 20th September, 2007
DOI: 10.3987/COM-07-S(W)13
Chalcogen Atom Competition in the Coordination of Bicyclic β-Lactam Derivatives to a Dirhodium Tetracarboxylate Complex

Edison Díaz Gómez, Jadwiga Frelek, Magdalena Woznica, Patrycja Kowalska, Jaroslaw Jazwinski, and Helmut Duddeck*

*Institute of Organic Chemistry, Leibniz University Hannover, Schneiderberg 1B, D-30167 Hannover, Germany

Abstract

NMR spectra of five enantiopure β-lactam derivatives with varying oxygen and sulfur atoms (1 to 5) have been recorded in the presence of an equimolar amount of a 2:1-mixture of (R)-Rh* and (S)-Rh* [(R/S)-Rh*]. No carboxylate ligand exchange between the two enantiomeric dirhodium complexes was observed. In general, sulfur is a much better donor than oxygen in axial coordination to rhodium. If both chalcogen atoms are equal (S in 1 and O in 4) the doubly bonded atom is the prefered binding site (C9=X). In the compounds with mixed chalcogen atoms, sulfur prevails as donor regardless of its bond order. This behaviour can be rationalized by comparing calculated molecular orbital energies and electronic charges. Olefinic groups do not contribute to binding significantly. All β-lactam derivatives were enantiopure so that it was possible to monitor significant chemical shift differences of the 1H, 13C and 19F NMR resonances for the two Rh* enantiomers. An experiment with racemic 4-vinyloxyazetidin-2-one (6) and (R)-Rh* suggests that the dirhodium method is effective for enantiodifferentiation of β-lactams.