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Bioconjugates of 1′‐Aminoferrocene‐1‐carboxylic Acid with ( S )‐3‐Amino‐2‐methylpropanoic Acid and L ‐Alanine
Author(s) -
Semenčić Mojca Čakić,
Heinze Katja,
Förster Christoph,
Rapić Vladimir
Publication year - 2010
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200901146
Subject(s) - chemistry , amino acid , peptidomimetic , alanine , intramolecular force , stereochemistry , ferrocene , stereocenter , carboxylic acid , combinatorial chemistry , organic chemistry , enantioselective synthesis , biochemistry , peptide , electrode , electrochemistry , catalysis
Formal CH 2 insertion in bioconjugates composed of 1′‐aminoferrocene‐1‐carboxylic acid (Fca) and alanine Boc‐Ala‐Fca‐Ala‐OCH 3 gives Fca bioconjugates with the β‐amino acid ( S )‐3‐amino‐2‐methylpropanoic acid (Aib). The novel homologous conjugates of ferrocene were fully characterized by spectroscopic and analytical methods. NMR, CD and IR spectroscopy in concert with DFT calculations suggest that the formal “ L ‐Ala–to–( S )‐β‐Aib mutations” can exert ferrocene helix inversion due to the different stereogenic carbon atoms of L ‐Ala and ( S )‐β‐Aib. Furthermore, the mutation (de‐)stabilizes the conserved secondary structure with two intramolecular hydrogen bonds, depending on the “mutation site”. The systematic work presented provides a firm basis for understanding the factors that determine folding in bioconjugates of ferrocene and β‐amino acids and will guide the rational design of metallocene peptidomimetics incorporating β‐amino acids.