title: Synthesis of penicillenol C1 and of a bis-azide analogue for photoaffinity labeling.
abstract: Two diasteroisomers of the Penicillium metabolite penicillenol C1 were synthesized for the first time by 3-acylation of an L-threonine-derived tetramic acid with enantiopure 2-methyloct-(6E)-enoic acids. The 5S,6R,9S isomer has NMR spectra and optical rotation identical with those of the natural compound. A bis-azide-tagged penicillenol analogue was also synthesized for photoaffinity labeling of target proteins. The photolysis of the bis-azide in the presence of methanol as a protein-mimicking nucleophile led to reaction only of the aryl azide, while leaving the benzyl azide available for pull-downs or the attachment of fluorescent tracers. As a proof of concept, the distribution of this bis-azide-tagged tetramic acid in living cells was visualized via a Staudinger ligation between the azide tag and a phosphane fluorophore.
authors: Organic Chemistry Laboratory, University Bayreuth, 95440 Bayreuth, Germany.
authors: Karl
authors: K
authors: Kempf
authors: Aruna
authors: A
authors: Raja
authors: Florenz
authors: F
authors: Sasse
authors: Rainer
authors: R
authors: Schobert
mesh_terms: D000215:Acylation; D000345:Affinity Labels / Q000138:chemical synthesis* / Q000737:chemistry; D001386:Azides / Q000138:chemical synthesis* / Q000737:chemistry*; D005456:Fluorescent Dyes / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D010782:Photolysis; D011760:Pyrrolidinones / Q000138:chemical synthesis* / Q000737:chemistry*; D013237:Stereoisomerism; D013912:Threonine / Q000737:chemistry* / Q000378:metabolism
chemical_list: D000345:Affinity Labels; D001386:Azides; D005456:Fluorescent Dyes; D011760:Pyrrolidinones; C584216:penicillenol C1; D013912:Threonine; C009435:tetramic acid