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Search for "glycerolipids" in Full Text gives 4 result(s) in Beilstein Journal of Organic Chemistry.
Synthesis of ether lipids: natural compounds and analogues
- Marco Antônio G. B. Gomes,
- Alicia Bauduin,
- Chloé Le Roux,
- Romain Fouinneteau,
- Wilfried Berthe,
- Mathieu Berchel,
- Hélène Couthon and
- Paul-Alain Jaffrès
Beilstein J. Org. Chem. 2023, 19, 1299–1369, doi:10.3762/bjoc.19.96
- correspond, for instance, to biosynthesized intermediates (e.g., 1-O-alkyl-glycerol-3-phosphate [4], lyso-PAF [5]) or neutral ether lipids (e.g., diacyl ether glycerol [6]). Ether glycerolipids are present in mammalian but also in anaerobic bacteria [7], archea (with an inverted stereochemistry at the sn-2
Graphical Abstract
Figure 1: Chemical structure of some natural ether lipids (ELs).
Figure 2: Synthesis of lyso-PAF and PAF from 1-O-alkylglycerol [64].
Figure 3: Synthesis of lyso-PAF from 1,3-benzylideneglycerol 3.1 [69].
Figure 4: A) Synthesis of the two enantiomers of octadecylglycerol (4.6 and 4.10) from ᴅ-mannitol (4.1); B) s...
Figure 5: Four-step synthesis of PAF 5.6 from (S)-glycidol [73].
Figure 6: Synthesis of 1-O-alkylglycerol A) from solketal, B) from ᴅ- or ʟ-tartaric acid and the intermediate ...
Figure 7: Synthesis of EL building blocks starting from substituted glycidol 7.1a–c [82].
Figure 8: Synthesis of PAF 8.5 by using phosphoramidite 8.2 [86].
Figure 9: Synthesis of oleyl-PAF 9.7 from ʟ-serine [88].
Figure 10: Synthesis of racemic analogues of lyso-PAF 10.8 and PAF 10.9 featuring a phenyl group between the g...
Figure 11: Synthesis of racemic deoxy-lyso-PAF 11.7 and deoxy-PAF 11.8 [91].
Figure 12: Synthesis of racemic thio-PAF 12.8 [93].
Figure 13: Racemic synthesis of 13.6 to illustrate the modification of the glycerol backbone by adding a methy...
Figure 14: Racemic synthesis of 14.5 as an illustration of the introduction of methyl substituents on the glyc...
Figure 15: Synthesis of functionalized sn-2-acyl chains of PC-EL; A) Steglich esterification or acylation reac...
Figure 16: Synthesis of racemic mc-PAF (16.3), a carbamate analogue of PAF [102].
Figure 17: A) Synthesis of (R)-17.2 and (S)-17.6 starting from (S)-solketal (17.1); B) synthesis of N3-PAF (17...
Figure 18: Modification of the phosphocholine polar head to produce PAF analogues [81].
Figure 19: Racemic PAF analogues 19.3 and 19.5 characterized by the absence of the phosphate group [107].
Figure 20: Synthesis of PIP3-PAF (20.7) [108].
Figure 21: Large-scale synthesis of C18-edelfosine (21.8) [116].
Figure 22: Synthesis of C16-edelfosine (22.10) starting from isopropylidene-ʟ-glyceric acid methyl ester (22.1...
Figure 23: Phosphocholine moiety installation by the use of chlorophosphite 23.2 as key reagent [119].
Figure 24: Synthesis of rac-1-alkyl-2-O-methylglycerol (AMG) [120].
Figure 25: Synthesis of stereocontrolled 1-alkyl-2-O-methyl glycerol 25.9 (AMG) from dimethyl ᴅ-tartrate [81].
Figure 26: A) Racemic synthesis of thioether 26.4 [129,130], B) structure of sulfone analogue 26.5 [129].
Figure 27: Stereocontrolled synthesis of C18-edelfosine thioether analogue 27.8 [118].
Figure 28: Synthesis of thioether 28.4 that include a thiophosphate function [134].
Figure 29: Synthesis of ammonium thioether 29.4 and 29.6 [135].
Figure 30: Synthesis of the N-methylamino analogue of edelfosine 30.6 (BN52211) [138].
Figure 31: Synthesis of 1-desoxy analogues of edelfosine; A) with a saturated alkyl chain; B) synthesis of the...
Figure 32: Stereocontrolled synthesis of edelfosine analogue (S)-32.8 featuring a C18:1 lipid chain [142].
Figure 33: Synthesis of edelfosine analogues with modulation of the lipid chain; A) illustration with the synt...
Figure 34: Synthesis of phospholipid featuring a carbamate function to link the lipid chain to the glycerol un...
Figure 35: Synthesis of sesquiterpene conjugates of phospho glycero ether lipids [148].
Figure 36: Racemic synthesis of methyl-substituted glycerol analogues 36.7 and 36.10: A) synthesis of diether ...
Figure 37: Racemic synthesis of ilmofosine (37.6) [155,156].
Figure 38: A) Stereoselective synthesis of 38.5 via a stereoselective hydroboration reaction; B) synthesis of ...
Figure 39: Racemic synthesis of SRI62-834 (39.6) featuring a spiro-tetrahydrofurane heterocycle in position 2 ...
Figure 40: Racemic synthesis of edelfosine analogue 40.5 featuring an imidazole moiety in sn-2 position [160].
Figure 41: Racemic synthesis of fluorine-functionalized EL: A) Synthesis of 41.6 and B) synthesis of 41.8 [161-163].
Figure 42: A) Synthesis of the β-keto-ester 42.6 that also features a decyl linker between the phosphate and t...
Figure 43: Synthesis of phosphonate-based ether lipids; A) edelfosine phosphonate analogue 43.7 and B) thioeth...
Figure 44: Enantioselective synthesis of phosphonates 44.3 and 44.4 [171].
Figure 45: Racemic synthesis of phosphinate-based ether lipid 45.10 [172].
Figure 46: Racemic synthesis of edelfosine arsonium analogue 46.5 [173].
Figure 47: Synthesis of edelfosine dimethylammonium analogue 47.2 [118].
Figure 48: Synthesis of rac-C18-edelfosine methylammonium analogue 48.4 [176].
Figure 49: A) Synthesis of edelfosine N-methylpyrrolidinium analogue 49.2 or N-methylmorpholinium analogue 49.3...
Figure 50: A) Synthesis of edelfosine’s analogue 50.4 with a PE polar group; B) illustration of a pyridinium d...
Figure 51: A) Synthesis of 51.4 featuring a thiazolium cationic moiety; B) synthesis of thiazolium-based EL 51...
Figure 52: Synthesis of cationic ether lipids 52.3, 52.4 and 52.6 [135,183].
Figure 53: Synthesis of cationic carbamate ether lipid 53.5 [184].
Figure 54: Synthesis of cationic sulfonamide 54.5 [185].
Figure 55: Chemical structure of ONO-6240 (55.1) and SRI-63-119 (55.2).
Figure 56: Synthesis of non-ionic ether lipids 56.2–56.9 [188].
Figure 57: Synthesis of ether lipid conjugated to foscarnet 57.6 [189].
Figure 58: A) Synthesis of ether lipid conjugated to arabinofuranosylcytosine; B) synthesis of AZT conjugated ...
Figure 59: Synthesis of quercetin conjugate to edelfosine [191].
Figure 60: Synthesis of 60.8 (Glc-PAF) [194].
Figure 61: A) Synthesis of amino ether lipid 61.7 functionalized with a rhamnose unit and its amide analogue 6...
Figure 62: A) Synthesis of glucose ether lipid 62.4; B) structure of ether lipid 62.5 possessing a maltose uni...
Figure 63: A) Synthesis of glucuronic methyl ester 63.8; B) structure of cellobiose 63.9 and maltose 63.10 ana...
Figure 64: A) Synthesis of maltosyl glycerolipid 64.7; B) structure of lactose analogue 64.8 prepared followin...
Figure 65: A) Asymmetric synthesis of the aglycone moiety starting from allyl 4-methoxyphenyl ether; B) glycos...
Figure 66: A) Synthesis of ohmline possessing a lactose moiety. B) Structure of other glyco glycero lipids pre...
Figure 67: A) Synthesis of lactose-glycerol ether lipid 67.5; B) analogues possessing a maltose (67.6) or meli...
Figure 68: Synthesis of digalactosyl EL 68.6, A) by using trityl, benzyl and acetyl protecting groups, B) by u...
Figure 69: A) Synthesis of α-ohmline; B) structure of disaccharide ether lipids prepared by using similar meth...
Figure 70: Synthesis of lactose ether lipid 70.3 and its analogue 70.6 featuring a carbamate function as linke...
Figure 71: Synthesis of rhamnopyranoside diether 71.4 [196].
Figure 72: Synthesis of 1-O-hexadecyl-2-O-methyl-3-S-(α-ᴅ-1'-thioglucopyranosyl)-sn-glycerol (72.5) [225].
Figure 73: A) Preparation of lipid intermediate 73.4; B) synthesis of 2-desoxy-C-glycoside 73.10 [226].
Figure 74: Synthesis of galactose-pyridinium salt 74.3 [228].
Figure 75: Synthesis of myo-inositol derivative Ino-C2-PAF (75.10) [230].
Figure 76: A) Synthesis of myo-inositol phosphate building block 76.7; B) synthesis of myo-inositolphosphate d...
Figure 77: A) Synthesis of phosphatidyl-3-desoxy-inositol 77.4; B) synthesis of phosphono-3-desoxyinositol 77.9...
Figure 78: A) Structure of diether phosphatidyl-myo-inositol-3,4-diphosphate 78.1; B) synthesis of phosphatidy...
Figure 79: A) Synthesis of diether-phosphatidyl derivative 79.4 featuring a hydroxymethyl group in place of a ...
Figure 80: Synthesis of Glc-amine-PAF [78].
Figure 81: Synthesis of glucosamine ether lipid 81.4 and its analogues functionalized in position 3 of the ami...
Figure 82: Synthesis of fully deprotected aminoglucoside ether lipid 82.5 [246].
Figure 83: Synthesis of C-aminoglycoside 83.12 using Ramberg–Bäcklund rearrangement as a key step [250].
Figure 84: A) List of the most important glyco lipids and amino glyco lipids included in the study of Arthur a...
Figure 85: Synthesis of mannosamine ether lipid 85.6 [254].
Figure 86: A) Synthesis of glucosamine ether lipids with a non-natural ʟ-glucosamine moiety; B) synthesis of e...
Figure 87: A) Structure of the most efficient anticancer agents 87.1–87.4 featuring a diamino glyco ether lipi...
Figure 88: A) Synthesis of diamino glyco ether lipid 87.4; B) synthesis of bis-glycosylated ether lipid 88.10 [256]....
Figure 89: Synthesis of triamino ether lipid 89.4 [260].
Figure 90: Synthesis of chlorambucil conjugate 90.7 [261].
Figure 91: Three main methods for the preparation of glycerol ether lipid 91.3; A) from solketal and via a tri...
Figure 92: Four different methods for the installation of the phosphocholine polar head group; A) method using...
Figure 93: Illustration of two methods for the installation of saccharides or aminosaccharides; A) O-glycosyla...
Synthesis of acylglycerol derivatives by mechanochemistry
- Karen J. Ardila-Fierro,
- Andrij Pich,
- Marc Spehr,
- José G. Hernández and
- Carsten Bolm
Beilstein J. Org. Chem. 2019, 15, 811–817, doi:10.3762/bjoc.15.78
- ]. Among the variety of amphipathic or hydrophobic small molecules that exhibit a lipid structure, diacylglycerols (DAGs) are important due to their signaling functions in cells (DAG signaling) [22][23][24]. Structurally, DAGs are glycerolipids containing two fatty acids esterified to the alcohol glycerol
Graphical Abstract
Figure 1: Biologically relevant molecules made, used or derivatized by mechanochemistry.
Figure 2: Isomeric diacyl-sn-glycerols (DAGs).
Scheme 1: Synthetic route to access protected DAGs; PG = protecting group.
Scheme 2: Protection of glycidol (1) with TBDMSCl in the ball mill. MM = mixer mill, PBM = planetary ball mil...
Scheme 3: Cobalt-catalyzed epoxide ring-opening in the ball mill.
Scheme 4: Mechanosynthesis of DAGs 5.
Scheme 5: Conjugation of DAG 5a with 7-hydroxycoumarin (9).
Figure 3: UV−vis spectra of DAG 6a (dotted line) and conjugated DAGs 10a and 10a’ as a mixture (10a/10a’ 72:2...
Remarkable functions of sn-3 hydroxy and phosphocholine groups in 1,2-diacyl-sn-glycerolipids to induce clockwise (+)-helicity around the 1,2-diacyl moiety: Evidence from conformation analysis by 1H NMR spectroscopy
- Yoshihiro Nishida,
- Mengfei Yuan,
- Kazuo Fukuda,
- Kaito Fujisawa,
- Hirofumi Dohi and
- Hirotaka Uzawa
Beilstein J. Org. Chem. 2017, 13, 1999–2009, doi:10.3762/bjoc.13.196
- of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, Tsukuba 305-8565, Japan 10.3762/bjoc.13.196 Abstract Cell-membrane glycerolipids exhibit a common structural backbone of asymmetric 1,2-diacyl-sn-glycerol bearing polar head groups in the sn-3 position. In this study, the possible
- ; deuterium labeling; sn-glycerol; glycerolipids; glycerophospholipids; helicity; Karplus equation; proton NMR spectroscopy; staggered conformers; Introduction Glycerophospholipids, constituting the basic elements of cytoplasm bilayer membranes, are responsible for several cell functions [1][2][3]. These
- representative model for the 1,2-diacyl-sn-glycerols, as categorized in Scheme 1. Although the exciton chirality CD methodology is not applicable for these 1,2-diacyl-sn-glycerolipids without an appropriate UV/CD chromophore, 1H NMR spectroscopy will permit the precise determination of their helical
Graphical Abstract
Figure 1: (a) Structures of cell-membrane glycerophospholpids with a common asymmetric 1,2-diacyl-sn-glycerol...
Scheme 1: The four 1,2-dipalmitoyl-sn-glycerols 1–4 examined in this study.
Figure 2: 1H NMR spectra of 1,2-dipalmitin (3) in CDCl3 after partial isomerization into the 1,3-isomer. (a) ...
Figure 3: Fractional populations (%) of the three staggered conformers around the sn-1,2 C–C single bond in 1...
Scheme 2: Structures of glycerophospholipids with a common structural skeleton of 1,2-dipalmitoyl-sn-glycerol...
Figure 4: Partial 1H NMR spectrum of 4 in a mixture of CDCl3 and methanol-d4 (C/M = 10:1, v/v).
Figure 5: Linear relation between the helical disparity (%) and gt(+) population (%) as observed for the heli...
Figure 6: An empirical diagram showing helical conformational properties around 1,2-diacyl moiety in asymmetr...
Scheme 3: Chirally 2H-labelled tripalmitins (1S)- and (1R)-1-[2H]-1 [23].
An easy α-glycosylation methodology for the synthesis and stereochemistry of mycoplasma α-glycolipid antigens
- Yoshihiro Nishida,
- Yuko Shingu,
- Yuan Mengfei,
- Kazuo Fukuda,
- Hirofumi Dohi,
- Sachie Matsuda and
- Kazuhiro Matsuda
Beilstein J. Org. Chem. 2012, 8, 629–639, doi:10.3762/bjoc.8.70
- glycerolipids 1H NMR spectroscopy provides a useful tool for discriminating between the two GGPL-I isomers as shown in Figure 2. A clear difference was observed in the chemical shifts of the glycerol methylene protons as designated by “a” and “b”. Conversely, little difference was observed between the sn
- conformers in equilibrated populations (gg = gt = tg). 3-O-(α-D-glucopyranosyl)-sn-glycerolipids 10 and 11 (Figure 3, entries 3 and 4) were found to have conformational properties very similar to DPPC; the lipid tail moiety prefers the gauche conformations (gt and gg), while the sugar moiety allows a random
- other 3-O-(α-D-glucopyranosyl)-sn-glycerolipids have a common conformational property at the chiral glycerol moiety: The lipid tail moiety prefers two gauche-conformations (gg and gt) in the order gt > gg >> tg, while the sugar head moiety adopts three conformers in an averaged population (gg = gt = tg
Graphical Abstract
Figure 1: Absolute chemical structures of M. fermentans α-glycolipid antigens, GGPL-I and GGPl-III (GGPL: Gly...
Scheme 1: An established synthetic pathway to α-glycosyl-sn-glycerols 4a and 5a. A reagent combination of CBr4...
Scheme 2: Syntheses of GGPL-I homologue I-a and its isomer I-b. Conditions: (a) K2CO3, CH3OH; (b) cesium palm...
Figure 2: 1H NMR spectra of I-a and I-b (500 MHz, 25 °C, CDCl3/CD3OD 10:1). The assignment of sn-glycerol met...
Figure 3: Distributions of gg, gt and tg-conformers in 3-substituted sn-glycerols at 11 mM in solutions of CD...
Figure 4: Distributions of gg, gt and tg-conformers in 1-substituted sn-glycerols. In these sn-isomers, Φ1 an...
Figure 5: A common conformational property of GGPL-I and DPPC. The tail lipid moiety favors two gauche-confor...
