15462-16-5Relevant academic research and scientific papers
Facilitating functionalization of benzene-1,3,5-tricarboxamides by switching amide connectivity
Dhiman, Shikha,Palmans, Anja R. A.,Schoenmakers, Sandra M. C.,Su, Lu,van den Bersselaar, Bart W. L.
supporting information, p. 8281 - 8294 (2021/10/12)
Synthetic water-compatible supramolecular polymers based on benzene-1,3,5-tricarboxamides (BTAs) have attracted a lot of interest in recent years, as they are uniquely suited to generate functional multicomponent biomaterials. Their morphologies and intrinsic dynamic behaviour mimic fibrous structures found in nature. Moreover, their modularity allows control of the density of functionalities presented on the surface of the fibres when using functionalized BTA monomers. However, such moieties generally comprise a functionality on only one of three side chains, resulting in lengthy synthetic protocols and limited yields. In this work, we avert the need for desymmetrization of the core by starting from commercially available 5-aminoisophthalic acid. This approach eliminates the statistical reactions and reduces the number of synthetic steps. It also leads to the inversion of the connectivity of one of the amides to the benzene core. By combining spectroscopy, light scattering and cryogenic transmission electron microscopy, we confirm that the inversed amide BTAs (iBTAs) form intermolecular hydrogen bonds and assemble into supramolecular polymers, like previously used symmetrical BTAs, albeit with a slight decrease in water solubility. Solubility problems were overcome by incorporating iBTAs into conventional BTA-based supramolecular polymers. These two-component mixtures formed supramolecular fibres with a morphology and dynamic behaviour similar to BTA-homopolymers. Finally, iBTAs were decorated with a fluorescent dye to demonstrate the synthesis of functional monomers, and to visualize their co-assembly with BTAs. Our results show that functionality can be introduced into supramolecular polymers with monomers that slightly differ in their core structure while maintaining the structure and dynamics of the fibres.
Chemical synthesis of diglucosyl diacylglycerols utilizing glycosyl donors with stereodirecting cyclic silyl protective groups
Takato, Koichi,Kurita, Motoki,Yagami, Nahoko,Tanaka, Hide-Nori,Ando, Hiromune,Imamura, Akihiro,Ishida, Hideharu
, (2019/08/01)
Chemical syntheses of the bacterial diglucosyl diacylglycerols 1-heptadecanoyl-2-pentadecanoyl-3-O-[6-O-(β-d-glucopyranosyl)-β-d-glucopyranosyl]-sn-glycerol and 1-(cis-13-octadecenoyl)-2-palmitoyl-3-O-[2-O-(α-d-glucopyranosyl)-α-d-glucopyranosyl]-sn-glycerol are described. The syntheses feature the stereoselective construction of glycosidic linkages in glycosylation reaction by utilizing glycosyl donors with stereodirecting cyclic silyl protective groups. The 1,1,3,3-tetraisopropyldisiloxane-1,3-diyl (TIPDS) group was used for formation of the β-glycosidic linkage, while the di-tert-butylsilylene (DTBS) group was used for α-linkage formation. The silyl protective groups were chemoselectively cleavable without affecting acyl functionalities on the glycerol moiety and proved effective for the synthesis of diacylglycoglycerolipids.
A Synthetic Route to the MT1-MMP Inhibitor Ancorinoside D
Petermichl, Markus,Steinert, Christine,Schobert, Rainer
, p. 730 - 738 (2019/01/23)
A methyl ester of ancorinoside D, a 3-acyltetramic acid metabolite of a sponge Penares sollasi, was synthesised in ten steps starting from a protected β- d -glucopyranosyl-(1→4)- d -galactopyranosyltrichloroacetimidate donor. Its attachment to the left half of the 3-acyl spacer by a Schmidt glycosylation, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated oxidation to the uronic acid, introduction of the Z -alkene via Wittig reaction, and functionalisation of the spacer terminus with Meldrum's acid gave a β-keto ester that reacted with dimethyl N -methyl- d -aspartate under neutral conditions to afford a fully protected ancorinoside D as the product of an unusual domino N -acylation-Dieckmann condensation. Global deprotection left a methyl ester of ancorinoside D, which resisted all saponification attempts.
Annonaceous acetogenin mimics bearing a terminal lactam and their cytotoxicity against cancer cells
Liu, Hai-Xia,Huang, Guo-Rui,Zhang, Huan-Ming,Wu, Jia-Rui,Yao, Zhu-Jun
, p. 3426 - 3430 (2008/02/09)
Annonaceous acetogenins are a large class of naturally occurring polyketides exhibiting potent anticancer activities. Based on our previous discovery of AA005, a multi-ether mimic of natural acetogenins having potent antitumor activities and significant selectivity between normal cells and cancer cells, a new series of mimics containing a terminal lactam were designed, synthesized and evaluated. Bioactivity study against cancer cells shows that the N-methylated lactam-containing compounds 3, 4, and 5 exhibit comparable potencies to that of AA005, as well as the similar selectivity to cancer cells. Hydrocarbon-length effects of N-alkyl were further explored through synthesizing derivatives 24-26, and application of this derivation protocol to the fluorescent labeling was also investigated.
Liquid crystalline properties of polyguanidines
Kim, Jeonghan,Novak, Bruce M.,Waddon, Alan John
, p. 8286 - 8292 (2007/10/03)
Modified polyguanidines were prepared, and their liquid crystalline properties were studied using optical polarizing microscopy and X-ray diffraction. Parameters examined include chirality, the uniformity of the lengths of side chains, and attached side-chain mesogens. If the side chains on the repeat units are identical, then polymer has a more ordered structure in both solution and the solid state. Uniform lengths of the side chains are also important. Poly(N,N′-di-n-hexylguanidine), poly-I, exhibited a lyotropic smectic texture in contrast to a nematic texture of poly(N-(rac)-2-phenylethyl)- N′-methylguanidine) (poly-(rac-II)). Optically pure poly(N-((R)-2- phenylethyl)-2-methylguanidine) (poly-(R-II)) formed a cholesteric texture, whereas the corresponding racemic polyguanidine, poly-(rac-II), formed a nematic texture. Additionally, poly-(R-II) displayed a mesophase at a lower critical concentration than either poly-I or poly-(rac-II), implying that poly-(R-II) is suffer than these two other derivatives. Polyu(N-6-((4′-methoxyphenylazo) phenyl-4-oxy)hexyl-N′-n-hexylguanidine) (poly-IV), one of combined liquid crystalline structures (liquid crystalline backbone plus liquid crystalline side chains), displayed a lyotropic nematic texture presumably due to the strong dipolar-dipolar interaction between the main chain and side chains that folds the appendages parallel to the molecular axis. Poly(N-12-((4′- methoxybiphenyl-4-oxy)dodecyl-N′-n-dodecylguanidine) (poly-V) and poly(N,N′-di-n-dodecylguanidine) (poly-VI) exhibited thermotropic liquid crystalline behavior.
Synthesis of two Unique Compounds, a Ceramide and a Cerebroside, Occurring in Human Stratum Corneum
Mueller, Silvia,Schmidt, Richard R.
, p. 779 - 784 (2007/10/03)
The cerebroside 1a and the ceramide 1b, both playing important roles in epidermal barrier function, were synthesized by N-acylation of 1-O-glucosylated C18-sphingosine 2 and C18-sphingosine 8, respectively, with O-acyl fatty acid 3. The required compound 3 was obtained from ω-hydroxy fatty acid 6 and linoleic acid 7 by esterification. The ω-hydroxy C30-fatty acid 6 was prepared as follows: Copper-catalyzed coupling of ω-hydroxy alkyl halide 11 with the Grignard reagent derived from bromo compound 13 afforded after oxidation C17-aldehyde 15. Wittig reaction with phosphonium salt 10, derived from ω-bromo-tridecanoic acid 9, and subsequent hydrogenation and O-deprotection furnished 6 in high yield.
