6076-30-8Relevant articles and documents
Nucleosides and nucleotides. 155. Synthesis, antitumor effects, and possible enzymatic activation mechanism of 5'-phosphatidyl-2'-deoxy-2'-methylenecytidine (DMDC)
Shuto, Satoshi,Awano, Hirokazu,Fujii, Akihiro,Yamagami, Keiji,Matsuda, Akira
, p. 2177 - 2182 (1996)
2'-Deoxy-2'-methylenecytidine (DMDC, 1) and its 5-fluoro congener (5-F-DMDC, 2), potent antitumor nucleosides developed by us, were efficiently converted to their 5'-phosphatidyl derivatives bearing palmitoyl residues (3 and 4, respectively) as novel antitumor phospholipids by phospholipase D-catalyzed trans-phosphatidylation. These phospholipids 3 and 4, administered i.p., remarkably prolonged the life-span of mice which were i.p.-inoculated with M5076 sarcoma, and the effects were clearly superior to that of DMDC. Compound 3 was a good substrate for phospholipase A2 from bovine pancreas as well as phospholipase D from Streptomyces, while it was slightly hydrolyzed by phospholipase C from Bacillus cereus.
Synthesis and enantiospecific analysis of enantiostructured triacylglycerols containing n-3 polyunsaturated fatty acids
Gudmundsson, Haraldur G.,Haraldsson, Gudmundur G.,Kallio, Heikki,Kalpio, Marika,Linderborg, Kaisa M.,Magnússon, Jóhann D.,Yang, Baoru
, (2020/07/08)
The stereospecific structure of triacylglycerols (TAGs) affects the bioavailability of fatty acids. Lack of enantiopure reference compounds and effective enantiospecific methods have hindered the stereospecific analysis of individual TAGs. Twelve novel enantiostructured AAB-type TAGs were synthesized containing one of the three n-3 polyunsaturated fatty acid: α-linolenic acid (ALA), eicosapentaenoic acid (EPA), or docosahexaenoic acid (DHA) in sn-1 or sn-3 position. These compounds formed six enantiomer pairs, which were separated with recycling high-performance liquid chromatography using chiral columns and UV detection. The chromatographic retention behavior of the enantiomers and the stereospecific elution order were studied. The enantiomer with an n-3 PUFA in the sn-1 position eluted faster than the enantiomer with the n-3 PUFA in the sn-3 position, regardless of the carbon chain length and number of double bonds of the PUFA. TAG enantiomers containing DHA exhibited highly different retention on the chiral column and were separated after the first column, whereas recycling was needed to separate the enantiomer pairs containing ALA or EPA. The system using two identical columns and one mobile phase, without sample derivatization, proved to be very effective also for peak purity assessment, confirming the enantiopurity of the synthesized structured TAGs being higher than 98 percent (96 percent ee).
Synthesis of enantiopure structured triacylglycerols
Kristinsson, Bjoern,Linderborg, Kaisa M.,Kallio, Heikki,Haraldsson, Gudmundur G.
, p. 125 - 132 (2014/02/14)
The synthesis of nine enantiopure structured triacylglycerols (TAGs) of the AAB type is described, all possessing the (S)-absolute configuration. Six of them possess one saturated and two identical unsaturated fatty acyl chains, whereas the remaining three possess two identical saturated fatty acids along with one unsaturated fatty acid. The former group was synthesized by a five-step chemoenzymatic route involving a highly regioselective immobilized Candida antarctica lipase, starting from enantiopure (R)-solketal. The second group was prepared by a fully chemical five-step approach based on the same chiral precursor. Such enantiopure TAGs are strongly required as standards for the enantiospecific analysis of intact TAGs in fats and oils.
4(2)-Methoxyphenyl glycerol ethers in the synthesis of nonracemic di-O,O-acylglycerols
Bredikhina,Novikova,Efremov,Sharafutdinova,Bredikhin
experimental part, p. 2320 - 2323 (2010/02/15)
Effective methods for the synthesis of nonracemic 4-and 2-methoxyphenyl glycerol ethers from nonracemic 3-chloropropanediols and by direct resolution of the racemate, respectively, were developed. Some existing discrepancies related to the to chiroptical properties of their derivatives were eliminated. Both ethers were used to synthesize nonracemic 3-O-aryloxy-1,2-di-O',O'-palmitoyl glycerols.
Glycerophosphoric acid ester derivative having polyfunctional metal chelate structure
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Page/Page column 14, (2008/06/13)
A compound represented by the following general formula (I), or a salt thereof: wherein R1 and R2 independently represent a substituted or unsubstituted alkyl or alkenyl group having 8 to 30 carbon atoms; L represents a divalent bridging group (L is constituted by atoms selected from the group consisting of carbon atom, oxygen atom, nitrogen atom and hydrogen atom, wherein the total number of atoms constituting L and selected from the group consisting of carbon atom, oxygen atom and nitrogen atom is 4 to 15); and Ch represents a chelate forming moiety containing 3 or more nitrogen atoms. A compound suitable for a liposome contrast medium for performing lesion-selective imaging is provided.
Synthesis of boron cluster lipids: Closo-dodecaborate as an alternative hydrophilic function of boronated liposomes for neutron capture therapy
Lee, Jong-Dae,Ueno, Manabu,Miyajima, Yusuke,Nakamura, Hiroyuki
, p. 323 - 326 (2008/02/03)
(Chemical Equation Presented) We succeeded in the synthesis of the double-tailed boron cluster lipids 4a-c and 5a-c, which have a B 12H11S moiety as a hydrophilic function, by S-alkylation of B12H11SH (BSH) with bromoacetyl and chloroacetocarbamate derivatives of diacylglycerols for a liposomal boron delivery system on neutron capture therapy. Calcein encapsulation experiments revealed that the liposomes, prepared from the boron cluster lipid 4b, DMPC, PEG-DSPE, and cholesterol, are stable at 37°C in FBS solution for 24 h.
A facile and convenient chemoenzymatic synthesis of optically active O-(4-methoxyphenyl)-glycidol and 1,2-diacyl-sn-glycerol
Kamal, Ahmed,Sandbhor, Mahendra,Shaik, Ahmad Ali,Malik, M. Shaheer
, p. 1855 - 1859 (2007/10/03)
A convenient preparation of the (R)- and (S)-enantiomers of O-(4-methoxyphenyl)-glycidol by a one-pot reduction of ketone 3 and in situ lipase mediated resolution is described. Activated moist aluminium oxide in the presence of Pseudomonas cepacia lipase immobilized on ceramic particles (PS-C) has been found effective for the transesterification leading to a high degree of enantioselectivity. These chiral glycidols were further used as a chiral precursor for the synthesis of biologically important 1,2-O-diacyl-sn-glycerol under mild reaction conditions. The present method is facile for the synthesis of chiral glycidols in high enantioselectivity when compared to the previously reported methods.
A new approach to the stereospecific synthesis of phospholipids. The use of L-glyceric acid for the preparation of diacylglycerols, phosphatidylcholines, and related derivatives
Roodsari, Farzaneh S.,Wu, Dongpei,Pum, Gregory S.,Hajdu, Joseph
, p. 7727 - 7737 (2007/10/03)
A new stereospecific synthesis of phospholipid derivatives of 1,2- diacyl-sn-glycerols is reported. The synthesis is based on (1) the use of L- glyceric acid as the stereocenter for construction of the optically active phospholipid molecule, (2) preparation of 3-triphenylmethyl-sn-glycerol as the key intermediate for sequential introduction of the primary and secondary acyl functions leading to the chiral diglycerides, and (3) elaboration of the sn-3-phosphodiester headgroup via phosphorylation using 2-chloro-2-oxo-1,3,2- dioxaphospholane, followed by ring opening of the five-membered phosphorus heterocycle with trimethylamine, ammonia, as well as oxygen and sulfur nucleophiles. The sequence has been shown to be suitable for the preparation of both symmetric and mixed-chain diacylglycerols with saturated and unsaturated acyl substituents. Phospholipid headgroups including phosphocholine, phosphoethanolamine, phosphoethanol, and phosphoethylthioacetate functions have been prepared. Application of the method to the synthesis of functionalized phosphatidylcholines has also been demonstrated by incorporating spectroscopically active spin-labeled and fluorescent reporter groups via postsynthetic derivatization of chain terminal ω-aminoalkyl functions of the acyl substituents of the compounds. The synthetic methods developed have a great deal of flexibility, providing convenient routes to a wide range of structurally variable phospholipids for physicochemical, enzymological, and cell-biological studies.
Asymmetric Total Synthesis of Phosphatidylinositol 3-Phosphate and 4-Phosphate Derivatives
Chen, Jian,Feng, Li,Prestwich, Glenn D.
, p. 6511 - 6522 (2007/10/03)
New asymmetric syntheses of phosphatidylinositol 3-phosphate (PtdIns(3)P) and phosphatidylinositol 4-phosphate (PtdIns(4)P) derivatives are described. Key intermediates were used to prepare diacylglyceryl moieties with dibutyryl, dioctanoyl, and dihexadecanoyl chains. In addition, a modified route provided PtdIns(3)P and PtdIns(4)P triesters with P-1-linked aminopropyl groups for preparation of affinity probes. The synthesis of the inosityl precursor employed a dibutyltin oxide-mediated p-methoxybenzyl (PMB) etherification to give either the 2-PMB- or the 3-PMB-protected glucopyranosides. The Ferrier rearrangement was used to convert suitably protected glucose derivatives to enantiomerically pure, differentially protected D-myo-inositol key intermediates. A versatile phosphoramidite reagent was employed to allow synthesis of PtdInsPn derivatives with diacylglyceryl moieties of different chain lengths.
The efficient synthesis of mixed diacyl phospholipids with polyunsaturated fatty acid in sn-2 position of glycerol
Xia, Jie,Hui, Yong-Zheng
, p. 3019 - 3021 (2007/10/03)
A convenient method for synthesis of the mixed-diacyl phospholipid using boron trichloride as an efficient reagent for the removal of benzyl protecting group from polyunsaturated diacylglycerols without affecting the double bond and acyl migration is desc
