2733-91-7Relevant articles and documents
Fat-derived aziridines and their N-substituted derivatives: Biologically active compounds based on renewable raw materials
Fuermeier, Sandra,Metzger, Juergen O.
, p. 649 - 659 (2003)
The first successful preparation of the aziridines methyl (9Z,12S,13R)-12,13-epimino-9-octadecenoate (10), derived from vernolic acid, and methyl (9R,10S,12R)-9,10-epimino-12-hydroxyoctadecanoate (12a) and methyl (9S,10R,12R)- 9,10-epimino-12-hydroxyoctadecanoate (12b), both derived from ricinoleic acid, is reported. These are the first examples of enantiomerically pure fat-derived aziridines. Treatment of the corresponding epoxides with sodium azide and ammonium chloride in ethanol in the presence of water yielded the new azido hydroxy compounds, which could be treated in an improved way with polymer-bound triphenylphosphane to afford the aziridines in good yields. The intermediate azido hydroxy compounds could easily be reduced and so offer access to a variety of interesting β-amino alcohols 17-21. The synthesis of various N-substituted aziridine derivatives 22-29 by treatment of methyl cis-9,10-epiminooctadecanoate (3) with phenyl isocyanate and isothiocyanate, acetyl chloride, alkyl and aryl chloroformates and acrylonitrile is described. Finally, the fat-derived 2,5 -dialkyl- substituted pyrrole methyl 9-(5-pentyl-1H-pyrrol-2-y1)nonanoate (9) was obtained. The previously reported bis(aziridine) methyl cis-9,10;cis-12,13-diepiminooctadecanoate, derived from linoleic acid, and tris-(aziridine) methyl cis-9,10;cis-12,13;cis-15,16-triepiminooctadecanoate, derived from linolenic acid,[1] have been subjected to different biological tests and showed cytotoxic and antimicrobial activity as well as remarkable antitumour-promoting and good neuroprotective effects. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.
Epoxidation of polyunsaturated fatty acid double bonds by dioxirane reagent: Regioselectivity and lipid supramolecular organization
Grabovskiy, Stanislav A.,Kabal'nova, Natalia N.,Chatgilialoglu, Chryssostomos,Ferreri, Carla
, p. 2243 - 2253 (2007/10/03)
The use of dimethyldioxirane (DMD) as the epoxidizing agent for polyunsaturated fatty acids was investigated. With fatty acid methyl esters, this is a convenient method for avoiding acidic conditions, using different solvents, and simplifying the isolation procedures, with less contamination due to by-products. The reagent was also tested with free fatty acids in water. In this case, the supramolecular organization of fatty acids influenced the reaction outcome, and the epoxidation showed interesting regioselective features. The C=C bonds closest to the aqueous-micelle interface is the most favored for the interaction with dimethyldioxirane. The preferential epoxidation of linoleic acid (=(9Z,12Z)-octadeca-9,12-dienoic acid) to the 9,10-monoepoxy derivative was achieved, with a high yield and 65% regioselectivity. In case of arachidonic acid (=(5Z,8Z,11Z,14Z)-eicosa-5,8,11,14-tetraenoic acid) micelles, the regioselective outcome with formation of the four possible monoepoxy isomers was studied under different conditions. It resulted to be a convenient synthesis of 'cis-5,6-epoxyeicosatrienoic acid' (=3-[(2Z,5Z,8Z)-tetradeca-2,5,8- trienyl]oxiran-2-butanoic acid), whereas in reverse micelles, epoxidation mostly gave 'cis-14,15-epoxyeicosatrienoic acid (= (5Z,8Z,11Z)-13-(3-pentyloxiran-2- yl)trideca-5,8,11-trienoic acid).
Structural Elucidation of Naturally Occurring 9,12,13-Trihydroxy Fatty Acids by a Synthetic Study
Kato, Tadahiro,Yamaguchi, Yoshihiro,Hirukawa, Toshifumi,Hoshino, Naoko
, p. 1349 - 1357 (2007/10/02)
Our investigation on anti-rice blast fungus materials from the rice plant has already led to the isolation of various types of oxygenated unsaturated fatty acids, which play an essential role in the defense of the rice plant against this fungus.Among those isolated were 9,12,13-trihydroxy C-18 fatty acids.We have determined the relative stereochemistry of the trihydroxy acid by synthesizing the possible stereoisomers.This paper describes the details of our synthetic study, demonstrating the fatty acid to be 9S,12S,13S-trihydroxyoctadeca-10E,15Z-dienoic acid and its 15-dihydro analogue.The absolute configuration was determined by observing a positive Cotton effect in the CD spectrum of the benzoate derivative of the natural material.
