Metal-induced chiral folding of depsipeptide dendrimers
Buschhaus B, Hampel F, Grimme S, Hirsch A (2005)
Publication Type: Journal article, Original article
Publication year: 2005
Journal
Original Authors: Buschhaus B., Hampel F., Grimme S., Hirsch A.
Publisher: Wiley-VCH Verlag
Book Volume: 11
Pages Range: 3530-3540
Journal Issue: 12
Abstract
The synthesis and metal complexation of chiral depsipeptide dendrimers 3 and 7 containing an ethylene-diaminetetraacetic acid (EDTA) esterderived core is reported. The EDTA ester cavity of these dendrimers selectively complexes Zn and Cu ions leading to diastereoselective folding. To elucidate the coordination motif in the resulting "foldamers" of 3-ZnCl, 7-ZnCl, 3-CuCl, and 7-CuCl the coordination behavior of the tetramethyl ester of EDTA (8) has been investigated as a model case. The corresponding complexes 8-ZnCl and 8-CuCl have been structurally characterized by H NMR spectroscopy and X-ray analysis. The complexes involve the inherently chiral octahedral cis-α coordination motif, in which 8 serves as a tetradentate ligand. In the case of the Zn complex 8-ZnCl , both Δcis-α(S,S,λ) and Λcis-α(R,R, λ.) stereoisomers were found in the unit cell. For the Cu complex 8-CuCl, only one stereoisomer, namely Δcis-α(S, S,λ.) was found in the crystal under investigation. H NMR spectroscopy has shown that the same coordination motif is diastereoselectively formed in the chiral Zn dendrimers 3-ZnCl and 7-ZnCl. Likewise, the calculated CD spectrum of the Δcis-α(S,S,λ) stereoisomer of the model complex 8-CuCl2 shows good agreement with the experimental spectrum of the Cu dendrimers 3-CuCl and 7-CuCl, allowing assignment of the absolute configurations of the preferred foldamers as Λcis-α(R,R,λ) for 3-CuCl and Δcis-α(S,S,λ) for 7-CuCl . This work represents the first example of metal-complexation- mediated diastereoselective folding of chiral dendrimers with known absolute configuration. © 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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APA:
Buschhaus, B., Hampel, F., Grimme, S., & Hirsch, A. (2005). Metal-induced chiral folding of depsipeptide dendrimers. Chemistry - A European Journal, 11(12), 3530-3540. https://doi.org/10.1002/chem.200401327
MLA:
Buschhaus, Boris, et al. "Metal-induced chiral folding of depsipeptide dendrimers." Chemistry - A European Journal 11.12 (2005): 3530-3540.
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