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Cα-Methyl, Cα-n-Propylglycine Homo-oligomers

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Institute of Biomolecular Chemistry, CNR, Department of Organic Chemistry, University of Padova, 35131 Padova, Italy
DSM Research, Life Sciences, Advanced Synthesis and Catalysis, P.O. Box 18, 6160 MD Geleen, The Netherlands
Laboratory of Crystallography, ESA 7036, Université Henry Poincaré−Nancy I, 54506 Vandoeuvre-lès-Nancy, France
Institute of Biostructure and Bioimaging, CNR, Interuniversity Research Center on Bioactive Peptides, University of Naples “Federico II”, 80134 Naples, Italy
Cite this: Macromolecules 2003, 36, 21, 8164–8170
Publication Date (Web):September 18, 2003
https://doi.org/10.1021/ma030327v
Copyright © 2003 American Chemical Society
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    Abstract

    A series of Nα-protected, monodispersed homo-oligopeptide esters to the octamer level from l-Cα-methyl, Cα-n-propylglycine [or Cα-methylnorvaline, (αMe)Nva] has been synthesized by solution methods and fully characterized. The preferred conformation of these homo-oligomers in solution has been assessed by FT-IR absorption and 1H NMR techniques. Moreover, the molecular structures of the homotrimer and homotetramer have been determined in the crystal state by X-ray diffraction. The obtained results strongly support the view that right-handed, single or multiple, and consecutive β bends are preferentially adopted by the conformationally restricted l-(αMe)Nva homo-oligomers. In particular, 310 helices are formed by the longest homo-oligomers. It is our contention that the [(αMe)Nva]n peptides represent the best available choice among Cα-tetrasubstituted α-amino acid-based homo-oligomers for the construction of relatively easy to make, rigid foldamers with a well-defined screw-sense bias.

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     To whom correspondence should be addressed. E-mail:  fernando.forma[email protected]. Tel (+39) 049-827-5277. Fax:  (+39) 049-827-5239.

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    Tables of positional parameters, bond distances, bond angles, and torsion angles for the X-ray diffraction structures of Z-[l-(αMe)Nva]3-OtBu and Z-[l-(αMe)Nva]4-OtBu. This material is available free of charge via the Internet at http://pubs.acs.org.

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