Preparation of macrocyclic 15N-labelled oligoaminodeoxysaccharides as probes for RNA-binding.
Two macrocyclic aminoglycosides were prepared from a 1,4-butanediol linked 2-deoxy-L-rhamnal which was O-allylated at the 4- and 4'-positions via the precursor allyl 3,4-di-O-acetyl-2,6-dideoxy-alpha-L-arabino-hexoside employing olefin metathesis and ring closing metathesis in a sequential manner. The macrocycles were 15N-labelled at all four amino groups in order to study interactions with regulatory RNA structures in solution by NMR spectroscopy. A key step for the introduction of the 15N-label was a reductive amination step using commercially available 15NH4OAc. The reductive amination proceeds with excellent stereocontrol. As a by-product the unusual acyclic amino nitrile was isolated which originated from intramolecular imine formation followed by cyanide addition to the intermediate C=N double bond.
Jaunzems
Janis
J
Institut für Organische Chemie der Universität Hannover, Schneiderberg 1B, D-30167, Hannover, Germany.
Oelze
Benjamin
B
Kirschning
Andreas
A
D000617:Aminoglycosides / Q000032:analysis / Q000138:chemical synthesis* / Q000737:chemistry / Q000378:metabolism*; D008968:Molecular Conformation; D015335:Molecular Probes / Q000032:analysis / Q000138:chemical synthesis* / Q000737:chemistry / Q000378:metabolism*; D015394:Molecular Structure; D009587:Nitrogen Isotopes; D009844:Oligosaccharides / Q000032:analysis / Q000138:chemical synthesis* / Q000737:chemistry / Q000378:metabolism*; D012313:RNA / Q000378:metabolism*
D000617:Aminoglycosides; D015335:Molecular Probes; D009587:Nitrogen Isotopes; D009844:Oligosaccharides; D012313:RNA