Iterative Synthese von Nukleosidoligophosphaten mit Phosphoramiditen

Cremosnik, Gregor S.; Hofer, Alexandre; Jessen, Henning J.

doi:10.1002/ange.201306265

Cited by 24 publications

(3 citation statements)

References 35 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Thes ynthesis of adenosine methylene triphosphate 21 was accomplished by the modification of amethod developed by us [22][23][24] and others for native pyrophosphates. [25] Partially protected methylene bisphosphonate 20 was first condensed with known bis[(methylsulfonyl)ethyl]diisopropylphosphoramidite (22) [26] in the presence of 5-ethylthiotetrazole (ETT) followed by in situ oxidation of the phosphonite-phosphonate anhydride intermediate by tBuOOH to give the protected precursor of 21. All steps could be monitored by 31 PNMR spectroscopy.…”

Section: Angewandte Chemiementioning

confidence: 99%

“…The four-cycle procedure started with coupling of the immobilized nucleoside with phosphanylmethylphosphonate reagent 18, with ETT as the activating agent. Subsequent oxidation with (1S)-(+ +)-(10-camphorsulfonyl)oxaziridine( CSO) yielded protected, resin-bound methylene bisphosphonate nucleotides 24.T he terminal tert-butyl groups in intermediate 24 were cleaved with HCl in HFIP (25), which was followed by DBU-mediated removal of the 2-cyanoethyl group.F inal aminolysis of the acyl protecting groups with concomitant release from the solid support was effected by treatment with aqueous ammonia. Thec rude products were purified by gel filtration, providing methylene bisphosphonate nucleotides 13 (39 %), 26 (46 %), 27 (44 %), and 28 (52 %).…”

Section: Angewandte Chemiementioning

confidence: 99%

See 1 more Smart Citation

Combined Phosphoramidite‐Phosphodiester Reagents for the Synthesis of Methylene Bisphosphonates

et al. 2017

View full text Add to dashboard Cite

A new class of phosphanylmethylphosphonate reagents has been developed to enable the controlled synthesis of methylene bisphosphonate mono- and diesters. Condensation of such reagents with an alcohol of choice through azole-mediated phosphoramidite chemistry followed by in situ oxidation provides orthogonally protected methylene bisphosphonate tetraesters. Global deprotection of the tetraester leads to terminal methylene bisphosphonates. Alternatively, selective deprotection at the terminal phosphonate followed by a condensation between the acquired methylene bisphosphonate triester and a second alcohol leads to methylene bisphosphonates diesters.

show abstract

Section: Angewandte Chemiementioning

confidence: 99%

Section: Angewandte Chemiementioning

confidence: 99%

Combined Phosphoramidite‐Phosphodiester Reagents for the Synthesis of Methylene Bisphosphonates

et al. 2017

View full text Add to dashboard Cite

show abstract

“…Since the custom bisfluorenylmethyl (bis-Fm) P-amidite reagent is not readily available and requires HPLC purification, we substituted a dibenzyl N , N -diisopropylphosphoramidite reagent as the phosphorus source for our research. 19 We assumed that benzyl (Bn) protection would make it easier to purify the phosphate intermediates by normal-phase silica gel chromatography, and that subsequent hydrogenation would result in the production of significant amounts of highly pure triphosphate compounds without the need for additional HPLC purification.…”

mentioning

confidence: 99%

Alternative Synthesis of α-l-Threofuranosyl Guanosine 3′-triphosphate

Sarma,

Majumdar,

Chaput

2023

Synlett

View full text Add to dashboard Cite

Artificial genetic polymers (XNAs) have attracted considerable attention due to their unique physicochemical properties that include enhanced chemical and biological stability. Unfortunately, some of the most interesting XNAs are constructed from monomers that are not readily available and must be prepared by chemical synthesis. The need to generate building-block materials for these systems warrants careful optimization, as syntheses of XNA monomers can easily exceed ten chemical steps. Here, we evaluate the synthesis of α-l-threofuranosyl guanosine 3′-triphosphate (tGTP), a key substrate in the enzymatic synthesis of α-l-threofuranosyl nucleic acids. Previously, tGTP was prepared by a Vorbrüggen glycosylation reaction from N-acetyl-O-(diphenylcarbamoyl)guanine and a suitably protected threose sugar. However, the preparation of the protected nucleobase was a laborious process that merited further evaluation. We now describe an alternative approach that is easier to perform and does not compromise the overall yield or regioselectivity.

show abstract

Facile and Efficient SynthesisofFluorene and Indenoarene Carboxylates from Biaryldiazoacetates via BlueLight‐promoted Intramolecular CarbeneC−H Insertion

et al. 2022

View full text Add to dashboard Cite

Inspired by the recent discovery that aryldiazoacetates could be excited with visible light to generate carbenes in a mild and catalyst‐free manner, we tested the possibility to induce the cyclization of fluorenes from biaryldiazoacetate precursors simply by visible light irradiation at ambient temperature. The experimental results showed that 455 nm blue light is most effective on the synthesis of a diversity of fluorenes and indenoarenes in excellent yields. Analysis of UV absorbance and electronic transition properties of biaryldiazoacetates revealed that their absorbance peaks in the blue light region are due to the n–π* transition of diazo group. Their small ϵ420 nm values well explains the fact that only when exposed to intense blue light could biaryldiazoaetates be excited to generate carbenes. Theoretical calculations and kinetic isotopic effect (KIE) study illustrated that the fluorene cyclization proceeds via the intramolecular carbene C−H insertion pathway rather than the cyclopropanation pathway. In addition, a furan ring‐opening mechanism for the unexpected formation of an indene‐based unsaturated aldehyde was also proposed based on the calculated potential energy surfaces of three plausible reaction pathways.

show abstract

Iterative Synthese von Nukleosidoligophosphaten mit Phosphoramiditen

Cited by 24 publications

References 35 publications

Combined Phosphoramidite‐Phosphodiester Reagents for the Synthesis of Methylene Bisphosphonates

Combined Phosphoramidite‐Phosphodiester Reagents for the Synthesis of Methylene Bisphosphonates

Alternative Synthesis of α-l-Threofuranosyl Guanosine 3′-triphosphate

Facile and Efficient SynthesisofFluorene and Indenoarene Carboxylates from Biaryldiazoacetates via BlueLight‐promoted Intramolecular CarbeneC−H Insertion

Contact Info

Product

Resources

About