Synthesis of Different 3,5‐Diazidofuranoses: A New and General Synthesis Pathway

Koth, Daniel; Fiedler, Andrea; Scholz, Sandy; Gottschaldt, Michael

doi:10.1080/07328300701540175

Cited by 7 publications

(6 citation statements)

References 14 publications

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“…Syntheses of 1 and 2 were previously published but were presently prepared using other reported procedures. − To a solution of 1 , ( 2 ) (500 mg, 1.9 mmol) in t -BuOH (5 mL) was added sodium ascorbate (263 mg, 1.3 mmol), copper(II) sulfate (160 mg, 0.7 mmol), and water (5 mL). After the change of color (white to purple), 2-ethynylpyridine (431 mg, 4.2 mmol) was added.…”

Section: Methodsmentioning

confidence: 99%

Sugars to Control Ligand Shape in Metal Complexes: Conformationally Constrained Glycoligands with a Predetermination of Stereochemistry and a Structural Control

et al. 2010

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In coordination chemistry, ligand shape can be used to tune properties, such as metal selectivity, coordination number, electronic structure, redox potential, and metal center stereochemistry including coordination helicates formation, and also to generate cavities for encapsulation. The results presented in this article indicate that two epimeric glycoligands (3 and 4) based on the conformationally restrained xylo- and ribo-1,2-O-isopropylidenefurano scaffolds are preorganized in water through pi-pi stacking due to hydrophobic interactions, as evidenced from excimer observation. The structure obtained in the solid state for one of the Cu(II) complexes (5) is chiral, with an original helical chirality arising from the coiling of the two ligands around the Cu-Cu axis. It shows an unusual double-deck type structure, with pi-pi interaction between two triazoyl-pyridyl rings and with a small cavity between the two Cu(II) ions able to host a bridging water molecule, as suggested by electron paramagnetic resonance. The Cu(II) complex from the epimeric ligand (6) shows similar properties with a mirror-image CD spectrum in the d-d region of the Cu(II). There is a predetermination of chirality at the metal center by the glycoligand induced by the C3 configuration, 6 and 5 being pseudoenantiomers. Interestingly, the stereochemistry at the metal center is here controlled by the combination of pi-stacking and chiral backbone.

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Section: Methodsmentioning

confidence: 99%

Sugars to Control Ligand Shape in Metal Complexes: Conformationally Constrained Glycoligands with a Predetermination of Stereochemistry and a Structural Control

et al. 2010

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“…[18,19] The synthesis pathway applied is much more efficient than the introduction of two amino groups into uridine in the 2',3'-position or into dribose or 2-deoxy-d-ribose, [20,21] because the thymine residue acts as a protecting group of the 3'-position during the synthesis (see Scheme S1 in the Supporting Information). For the preparation of the platinum (3 and 5) and palladium complexes (4 and 6) an aqueous solution of potassium tetrachloroplatinate or potassium tetrachloropalladinate, respectively, was added dropwise into a boiling solution of the amine (1 or 2) in water (Scheme 1).…”

Section: Resultsmentioning

confidence: 99%

“…Synthesis and structural characterization of the complexes : The two 3′,5′‐diamino‐3′,5′‐dideoxy‐thymidines ( 1 and 2 ) were previously obtained as intermediates for the synthesis of metal complexes based on their condensation products with salicyliden aldehydes 18. 19 The synthesis pathway applied is much more efficient than the introduction of two amino groups into uridine in the 2′,3′‐position or into D ‐ribose or 2‐deoxy‐ D ‐ribose,20, 21 because the thymine residue acts as a protecting group of the 3′‐position during the synthesis (see Scheme S1 in the Supporting Information). For the preparation of the platinum ( 3 and 5 ) and palladium complexes ( 4 and 6 ) an aqueous solution of potassium tetrachloroplatinate or potassium tetrachloropalladinate, respectively, was added dropwise into a boiling solution of the amine ( 1 or 2 ) in water (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

Mitochondrial Mode of Action of a Thymidine‐Based Cisplatin Analogue Breaks Resistance in Cancer Cells

Onambele

Koth

Czaplewska

et al. 2010

Chemistry A European J

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Cisplatin analogue complexes with platinum(II) and palladium(II) starting from 3',5'-diamino-3',5'-dideoxy-thymidines were synthesized, both with the D-erythro- and D-threo configurations. Complexes of the general formula [MCl(2)L] were obtained and characterized. NMR spectroscopic measurements and single crystal X-ray structure analysis showed that the metal centers are coordinated to the ligands by the amino groups in 3'- and 5'-positions and not through the thymine moiety. All ligands and complexes showed no significant in vitro activities except thymiplatin (cis-dichloro(3',5'-diamino-3',5'-dideoxy-D-threo-thymidine)platinum(II)). Detailed in vitro studies on the apoptosis pathway in lymphoma (BJAB), leukemia (NALM-6), and melanoma cells (Mel-HO) as well as on transfected or resistant cell lines were carried out. Thymiplatin significantly induced an apoptotic response, which was found to be associated with the loss of mitochondrial membrane potential and with caspase activation. The activity was shown to be independent of Fas-associated protein with death domain (FADD), but dependent on Bcl-2 expression. As a consequence, for thymiplatin a mitochondrial mode of action could be assigned. Moreover, the compound showed activity in cells resistant to common drugs, such as daunorubicin and vincristin, and showed synergistic effects with doxorubicin, vincristin, cytarabin, and daunorubicin.

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“…Then we started to synthesize glycosylation donor 16 as the key building block ( Scheme 2 ). In previous reports, 3,5- O -diacetyl-1,2- O -isopropylidene-D-ribofuranose ( 11 ) was prepared either from D-xylose [ 29 – 31 ] or from tetra- O -acetyl-β-D-ribose ( 10 ) [ 32 – 33 ]. In 2009, Koreeda reported an iodine-promoted acetonide-forming reaction of tetra- O -acetyl-β-D-ribose ( 10 ) [ 33 ].…”

Section: Resultsmentioning

confidence: 99%

First total synthesis of kipukasin A

Li¹,

Ding²,

Ruan³

et al. 2017

Beilstein J. Org. Chem.

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In this paper, a practical approach for the total synthesis of kipukasin A is presented with 22% overall yield by using tetra-O-acetyl-β-D-ribose as starting material. An improved iodine-promoted acetonide-forming reaction was developed to access 1,2-O-isopropylidene-α-D-ribofuranose. For the first time, ortho-alkynylbenzoate was used as protecting group for the 5-hydoxy group. After subsequent Vorbrüggen glycosylation, the protecting group could be removed smoothly in the presence of 5 mol % Ph3PAuOTf in dichloromethane to provide kipukasin A in high yield and regioselectivity.

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Synthesis of Different 3,5‐Diazidofuranoses: A New and General Synthesis Pathway

Cited by 7 publications

References 14 publications

Sugars to Control Ligand Shape in Metal Complexes: Conformationally Constrained Glycoligands with a Predetermination of Stereochemistry and a Structural Control

Sugars to Control Ligand Shape in Metal Complexes: Conformationally Constrained Glycoligands with a Predetermination of Stereochemistry and a Structural Control

Mitochondrial Mode of Action of a Thymidine‐Based Cisplatin Analogue Breaks Resistance in Cancer Cells

First total synthesis of kipukasin A

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