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1.
An efficient multigram scale synthesis of a new asymmetric triazacyclophane scaffold, the ATAC (Asymmetric-TAC) scaffold, bearing three selectively removable groups is described. This scaffold is slightly more rigid than our frequently used TAC (TriAzaCyclophane) scaffold. The synthesis of the required triamine is very high yielding without difficult steps or purifications and was also applied to a much improved synthesis of our original TAC scaffold. Especially the tedious first reaction step, that is, mono-oNBS-protection of a triamine could be omitted. The rigidity of the triazacyclophane ring in both TAC- and ATAC scaffolds has also been investigated using variable temperature 1H NMR experiments. 相似文献
2.
The synthesis of a polypseudorotaxane, polyrotaxane, and polycatenane containing the electron-deficient cyclophane cyclobis(paraquat-p-phenylene) (CBPQT4+) subunit in the side chain is described. These interlocked supramolecular polymers have been prepared from an azide-functionalized polystyrene derivative and an acetylene-functionalized [2]rotaxane, [2]catenane and their parent tetracationic cyclophane via Cu(I)-catalyzed 1,3 dipolar cycloadditions (‘click chemistry’). The synthesis and characterization of the polymers and intermediates has been described using IR, 1H NMR, UV spectroscopies, and voltammetry. We have shown that the CBPQT4+ unit of the side chain polystyrene derivative has the ability to reversibly undergo complexation with a complementary dialkoxynaphthalene derivative. 相似文献
3.
Hiroshi Tanaka Prof. Dr. Yoshio Ando Dr. Tsutomu Abe Dr. Takashi Takahashi Prof. Dr. 《化学:亚洲杂志》2008,3(12):2033-2045
An effective hydrophilic scaffold composed of D ‐trihydroxyllysine‐based oligopeptides and its application in the synthesis of the various 111In–DTPA conjugates with mono‐ to penta‐bisphosphonate units for use as bone tracers are described. The D ‐trihydroxyllysine derivative with three orthogonal protecting groups was conjugated with functional devices at the γ position and allowed oligomerization based on peptide chemistry. The radiopharmaceutical complexes of 111InIII with selected chelators, 4 and 8 , were suitable for bone imaging. These results show that D ‐trihydroxyllysine 2 was an effective building block for the synthesis of multivalent ligands applicable to medical use. 相似文献
4.
Andrew M. Steer Hannah L. Bolt William D.G. Brittain Steven L. Cobb 《Tetrahedron letters》2018,59(27):2644-2646
Herein the synthesis of an Fmoc/OtBu orthogonally protected iodotyrosine derivative is reported. This has been achieved via a simple two-step process in an overall 58% yield from commercially available Fmoc-Tyr(tBu)-OH. The Fmoc/OtBu orthogonally protected iodotyrosine was also shown to be amenable to Suzuki-Miyaura cross-coupling to deliver a novel bi-aryl tyrosine derivative. 相似文献
5.
Herein, we report a novel approach for the synthesis of π-conjugated peptide-based donor-acceptor (D-π-A) chromophores, by reacting electron-rich alkynes with tetracyanoethylene. The desired tetracyanobutadiene-scaffolded peptides were obtained in good yields with various optical properties, λmax: 321-492 nm, ε: 21,000-65,000 mol−1 dm3 cm−1 depending on the substitution pattern of the cyanobutadiene scaffold. 相似文献
6.
Polyamines are highly attractive vectors for tumor targeting, particularly with regards to the development of radiolabeled probes for imaging by positron emission (PET) and single-photon emission computed tomography (SPECT). However, the synthesis of selectively functionalized derivatives remains challenging due to the presence of multiple amino groups of similar reactivity. In this work, we established a synthetic methodology for the selective mono-fluorobenz(o)ylation of various biogenic diamines and polyamines as lead compounds for the perspective development of substrate-based radiotracers for targeting polyamine-specific membrane transporters and enzymes such as transglutaminases. For this purpose, the polyamine scaffold was constructed by solid-phase synthesis of the corresponding oxopolyamines and subsequent reduction with BH3/THF. Primary and secondary amino groups were selectively protected using Dde and Boc as protecting groups, respectively, in orientation to previously reported procedures, which enabled the selective introduction of the reporter groups. For example, N1-FBz-spermidine, N4-FBz-spermidine, N8-FBz-spermidine, and N1-FBz-spermine and N4-FBz-spermine (FBz = 4-fluorobenzoyl) were obtained in good yields by this approach. The advantages and disadvantages of this synthetic approach are discussed in detail and its suitability for radiolabeling was demonstrated for the solid-phase synthesis of N1-[18F]FBz-cadaverine. 相似文献
7.
Andrea TrabocchiGloria Menchi Massimo RollaFabrizio Machetti Ilaria BucelliAntonio Guarna 《Tetrahedron》2003,59(28):5251-5258
New methodology for the synthesis of enantiopure 3-aza-6,8-dioxa-bicyclo[3.2.1]octane-carboxylic acids belonging to 7-endo-BTAa sub-class of γ/δ amino acids is described. The novelty is the use of 2,3-O-isopropylidene-erythrose instead of meso-tartaric acid derivative, thus allowing us to perform an enantiospecific synthesis. Reductive amination of erythrolactol with aminoacetaldehyde diethylacetal or benzylamine, and subsequent acid cyclisation gave directly the amino alcohol scaffold. Protection of nitrogen as urethane and final alcohol oxidation afforded the Fmoc-, Boc-, and Cbz-amino acids. The new synthetic route was applied to multigram scale, thus resulting in a marked improvement of the synthesis of enantiopure 7-endo-BTG and 7-endo-BTK amino acids. 相似文献
8.
A novel and convenient method for the synthesis of C-terminally branched collagen-model peptides has been achieved using tricine (N-[tris(hydroxymethyl)methyl]glycine) as a branching scaffold and 1,2-diaminoethane or 1,4-diaminobutane as a linker. The peptide sequence was incorporated directly onto the linker and scaffold during solid-phase synthesis without additional manipulations. The resulting branched triple-helical peptides exhibited comparable thermal stabilities to the parent, unbranched sequence, and served as substrates for matrix metalloproteinase-1 (MMP-1). The tricine-based branch reported herein represents the simplest synthetic scaffold for the convenient synthesis of covalently linked homomeric collagen-model triple-helical peptides. 相似文献
9.
Crina Cisma? 《Tetrahedron letters》2008,49(8):1336-1339
An alternative route for the synthesis of a photoaffinity labelling (PAL) dCTP derivative is reported. This method involves the intermediacy of exo-N-[2-(4-azido-2,3,5,6-tetrafluorobenzamido)ethyl]-dC. The latter is prepared from the coupling of known N-(2-aminoethyl)-4-azido-2,3,5,6-tetrafluorobenzamide, prepared in an improved three-step sequence, with an activated 4-triazolyl derivative of dU, followed by deprotection. 19F NMR spectroscopy proved extremely useful in following the synthetic transformations, and enabled control of any adventitious reduction of the azides. 相似文献
10.
An efficient and practical method for the large-scale synthesis of an anti-inflammatory glycocluster having seven sialyl Lewis X (SLeX) residues was established on the basis of chemical and enzymatic strategy from β-cyclodextrin (β-CD) as a key starting scaffold material. A key intermediate, β-CD derivative having seven N-acetyl-d-glucosamine (GlcNAc) residues [(GlcNAc)7CD], was prepared by a coupling reaction with heptakis 6-deoxy-6-iodo-β-cyclodextrin and sodium thiolate containing a GlcNAc residue. Subsequent sugar elongation reactions of (GlcNAc)7CD proceeded smoothly by means of β-1,4-galactosyltransferase, α-2,3-sialyltransferase, and α-1,3-fucosyltransferase V in the presence of the corresponding sugar nucleotides (UDP-Gal, CMP-Neu5Ac, and GDP-Fuc) and allowed to give a mono-dispersed glycodendrimer (Mw=7924.5, calcd for C301H490N21O196S7Na7; MALDI-TOF MS, m/z 7946 [M+Na]+) that completely substituted with seven SLeX branches at C-6 positions in excellent overall yield (74%, 3 steps). Hyper-branched glycodendrimer, (SLeX)7CD, exhibited highly amplified inhibitory effect on the interaction of E-selectin with SLeXn-BSA immobilized on the sensor chip by means of surface plasmon resonance method. 相似文献
11.
Hai-Xia Liu 《Tetrahedron letters》2005,46(20):3525-3528
Annonaceous acetogenins are a series of potent naturally occurring anticancer agents, which act as inhibitors of complex I in mitochondria. AA005, a mimicry of acetogenins, has been found as active as those natural products and to present high selectivities between cancer and normal cells. In order to investigate the further cell-based mechanism induced by AA005, a d4-labeled derivative of AA005 (AA005-d4) was designed to detect the drug permeation ability into the membranes. In this letter, the synthesis is reported of this deuterium-labeled compound, wherein a ethylene-d4 glycol unit is incorporated efficiently into the molecule skeleton by simple etherifications. 相似文献
12.
A novel siderophore analog (4) has been designed to facilitate iron transport-mediated drug delivery and drug release. This mixed ligand siderophore analog includes three bidentate ligands intended to octahedrally coordinate iron (III). The ligands include a 2,3-dihydroxy benzoic acid moiety, N5-acetyl-N5-hydroxy-l-ornithine, and a β-N-hydroxy-α,β-diaminopropionic acid derivative. The total synthesis of 15, a form of 4 that is suitably protected, yet contains a free carboxylic acid for subsequent drug conjugation, is described. 相似文献
13.
《Analytica chimica acta》1987,203(1):85-89
The fluorescent 14-crown-4 derivative possesses a p-(1,8-naphthalenedicarboxi-mido) phenol moiety as the proton -dissociable fluorophore; its synthesis is described. Highly selective extraction of lithium is achieved with the crown ether, based on a proton/metal ion-exchange mechanism. Extraction is accompanied by significant changes in the absorption and fluorescence spectra of the organic phase. Extraction equilibrium constants for the lithium and sodium ions are evaluated, the Li+/Na+ selectivity ratio being 200; other alkali metal ions were not extracted. The Li+ extraction quenched the fluorescence intensity of the crown ether, in correlation with the initial cation concentration in the aqueous phase. 相似文献
14.
Esther Alza Luca Laraia Brett M. Ibbeson Súil Collins Warren R. J. D. Galloway Jamie E. Stokes Ashok R. Venkitaraman David R. Spring 《Chemical science》2015,6(1):390-396
The synthesis of a previously undescribed sp3-rich 6-5-5-6 tetracyclic ring scaffold using a palladium catalysed domino Heck–Suzuki reaction is reported. This reaction is high-yielding, selective for the domino process over the direct Suzuki reaction and tolerant towards a variety of boronic acids. The novel scaffold can also be accessed via domino Heck–Stille and radical cyclisations. Compounds based around this scaffold were found to be effective antimitotic agents in a human cancer cell line. Detailed phenotypic profiling showed that the compounds affected the congression of chromosomes to give mitotic arrest and apoptotic cell death. Thus, a novel structural class of antimitotic agents that does not disrupt the tubulin network has been identified. 相似文献
15.
Chigalli N. Revanna Goravanahalli M. Raghavendra Kebbahalli N. Nandeesh Doddamedur G. Bhadregowda Kanchugarakoppal S. Rangappa Kempegowda Mantelingu 《Tetrahedron letters》2013
5-Allyl-7,7-difluoro-2-(2,4-difluorophenyl)-6-(4-methoxyphenyl)-4,5,6,7-tetrahydro-2H-pyrazolo[4,3-c]pyridine-3-amine represents a fluorinated heterocyclic scaffold, potentially attractive. It was synthesized via Michael addition, Mannich reaction of the difluorinated ethyl bromoacetate with a benzotriazole derivative, followed by a Dieckmann condensation. Starting from simple materials, this efficient route which gives access to novel functionalized N-(5-allyl-7,7-dihalo)-4,5,6,7-tetrahydro-2H-indazol-3-yl)-carboxymides, was explored and adapted for parallel synthesis, resulting in a compound library. 相似文献
16.
The chemical synthesis and 1H NMR analysis of a novel bicyclic uridine derivative, with a 18-crown-6 ether moiety fused at the ribose 2- and 3-positions, as first example of a hitherto unknown class of ribose-modified nucleosides, are here described. NMR-based conformational analysis studies showed for the modified nucleoside a marked preference for an N-type sugar puckering and the nucleobase in the anti conformation, with the uracil favouring the coordination of a sodium ion hosted in the crown ether. 相似文献
17.
The synthesis of two oligomers, of a bifunctional diketopiperazine scaffold DKP-1, formally derived from the cyclization of l-aspartic acid and (S)-2,3-diaminopropionic acid, is reported. A trimeric and a tetrameric structure were prepared by solution-phase peptide synthesis (Boc strategy). Conformational analysis of these derivatives was carried out by a combination of 1H NMR spectroscopy, CD spectroscopy, and molecular modeling, and revealed the formation of β-bend ribbon involving 10-membered H-bonded rings and a reverse turn of the growing peptide chain. 相似文献
18.
A. O. Kharaneko 《Russian Journal of Organic Chemistry》2017,53(5):738-745
A strategy was developed for the synthesis of 7,8,9-trimethyl-1-phenyl-3H-pyrrolo[2,1-d][1,2,5]-triazepin-4(5H)-one, reactions of its functionalization at the С4 atom and aza rings fusion at the С4?N3 bond were explored. The formation mechanism of the pyrrolo-1,2,5-triazepinone scaffold was suggested. 相似文献
19.
Marcel Špulák Zdeněk Novák Karel Palát Jiří Kuneš Jana Pourová Milan Pour 《Tetrahedron》2013,69(6):1705-1711
Contrary to a number of reports, alkylations of the privileged 3,4-dihydroquinazoline scaffold provide N3-alkylated products, and not 4-alkoxyquinazolines. To correctly assign the structure, 13C NMR shifts of the –Z–CHn– (Z=O, N) fragment are necessary; resonances in the 45–55 ppm range are indicative of N3-alkylation. Treatment of 3,4-dihydroquinazoline-4-one with p-TsCl afforded the N3-tosylated compound, whose reaction with an amine yielded the corresponding N3-alkyl derivative. A mechanism corroborated by 15N-labeling involving pyrimidine ring opening and recyclisation is proposed. Finally, the unambiguous preparation of 4-alkoxyquinazolines is described via treatment of 3,4-dihydroquinazoline-4-ones with PCl5 followed by an alkoxide. 相似文献
20.
Kosuke Okuma Akira M. Ono Makoto Oba Masatsune Kainosho Tsutomu Terauchi 《Tetrahedron letters》2009,50(13):1482-163
We have developed a synthetic route for (2S,3R)- and (2S,3S)-[2-13C;3-2H] glutamic acids with high enantioselectivity. The key reactions in this synthesis are the asymmetric reduction of the 2,3-didehydroornithine derivative using the (S,S)-Et-DuPHOS-Rh catalyst and the oxidation of the δ-position by ruthenium catalysis. 相似文献