644. Nucleotides. Part XLI. Mixed anhydrides as intermediates in the synthesis of dinucleoside phosphates

Hall, Ross H.; Todd, A. R.; Webb, R. F.

doi:10.1039/jr9570003291

Cited by 74 publications

(48 citation statements)

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“…The product was finally recrystallized from absolute ethanol. Yield: 17.8 1 Compound 3 (0.89 g, 1.1 mmol) and 2,3-di-0-benzoyluridine (0.45 g, 1 mmol) were coevaporated with pyridine and dissolved in the same solvent (10 ml). To the stirred reaction mixture bis(2-oxo-3-oxazolidinyl)phosphinic chloride25 (OXP)(0.64 g, 2 mmol) was then added.…”

Section: Synthesis Of 2'3'-di-o-benzoyluridinementioning

confidence: 99%

Studies on the t-butyldimethylsilyl group as 2'-O-protection in oligoribonucleotide synthesis via the H-phosphonate approach

et al. 1988

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Two model compounds, 1 and 2, have been studied to test the stability of the t-butyldimethylsilyl (t-BDMSi) group towards conditions used during chemical synthesis of RNA fragments by the H-phosphonate approach. When 1 was treated with anhydrous acid for 16 h both the H-phosphonate diester and the t-BDMSi group remained intact. Removal of the t-BDMSi group from 2 with 1.0 M tetrabutylammonium fluoride (TBAF -3H20) in THF was complete within 4 h and neither concomitant cleavage nor migration of the phosphodiester linkage could be detected even after 24 h. The dimer 2 was not completely stable towards concentrated aqueous ammonia and both loss of the t-BDMSi group and concomitant cleavage of the phosphodiester linkage occurred upon prolonged treatment. These reactions were substantialy suppressed in ethanol containing ammonia solutions, however to alleviate this problem during oligoribonucleotide synthesis, more labile protecting groups for heterocyclic bases would be desired. In conclusion, these studies indicate that 2 -O-t-BDMSi can be considered as a convenient and safe protecting group, which should secure synthesis of oligoribonucleotides with exclusively 3'-5' internucleotidic linkages.

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Section: Synthesis Of 2'3'-di-o-benzoyluridinementioning

confidence: 99%

Studies on the t-butyldimethylsilyl group as 2'-O-protection in oligoribonucleotide synthesis via the H-phosphonate approach

et al. 1988

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“…While H-phosphonate chemistry was introduced to nucleotide field by Sir Todd in 1957, [1] the modern approach to internucleotide bond formation by H-phosphonate method dates back to 1985-1986 and papers by Stawinski [2] and Froehler. [3] Due to these works, H-phosphonates emerged as particularly efficient and versatile precursors for preparation of many biologically active phosphorus compounds.…”

Section: Introductionmentioning

confidence: 99%

Stereochemistry of Internucleotide Bond Formation by theH-Phosphonate Method. 5. The Role of Brønsted and H-Bonding Base Catalysis in RibonucleosideH-Phosphonate Condensation—Chemical and Stereochemical Consequences

Sobkowski

Stawiński

Kraszewski

2010

Nucleosides, Nucleotides and Nucleic Acids

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Efficiency and stereoselectivity of condensations of ribonucleoside 3'-H-phosphonates with ethanol promoted by pivaloyl chloride were investigated as a function of tertiary amines used. Side reactions leading to an increased demand for the condensing agent were identified as derived from an attack of the pivalate anion at carbonyl centers of reactive pivaloyl derivatives. The conditions that secured quantitative yields of H-phosphonate diester condensations were assessed. Several tertiary amines promoted condensations with stereoselectivity higher than that observed for pyridine derivatives. A correlation between diastereoselectivity of the product formation and Brønsted and H-bonding basicities of the amine used was found.

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“…5). The H -p h o sp h o n ate approach [9] uses the sam e solid supports and protecting groups for the am ino functions on the bases and 5 '-hydroxyl groups of the nucleoside moiety. A fter detrity la tion, the subsequent p ro tected H -p h osphonate is delivered in presence of an acid chloride (e.g.…”

Section: Introductionmentioning

confidence: 99%

Optimized Automated Solid Phase Synthesis of Oligonucleotides and Derivatives

Urbina

Grübler

Weiler

et al. 1998

Zeitschrift Für Naturforschung B

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G abriel A lv arad o U rb in a 3, G erald G rü b le r3, A ngelika W eilerb, H artm u t E c h n erb, Stanka S toevab, Jo h an n S ch ern th an er3, W aleri G ross3, W olfgang V oelterb * Oligonucleotides, Thio-Oligonucleotides, 5'-and 3'-Derivatisation of Oligonucleotides, Automatic O ligonucleotide Synthesis, G ene Assembly An optimized autom ated synthesizer is presented for assembling oligonucleotides, thiooligonucleotides and 5'-m odified oligonucleotides including: chemical phosphorylation, multihydroxyl derivatization with a non-nucleosidic phosphoramidite. The incorporation of biotin, fluorescein and rhodamine phosphoramidites is described. The purification and struc ture determination o f oligo-nucleotides was confirmed using high performance liquid chro matography (H PLC ), capillary electrophoresis (CE) and laser desorption mass spectrometry (LD M S). Several applications and confirming data polymerase chain reaction (PCR) experiments.

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644. Nucleotides. Part XLI. Mixed anhydrides as intermediates in the synthesis of dinucleoside phosphates

Cited by 74 publications

References 0 publications

Studies on the t-butyldimethylsilyl group as 2'-O-protection in oligoribonucleotide synthesis via the H-phosphonate approach

Studies on the t-butyldimethylsilyl group as 2'-O-protection in oligoribonucleotide synthesis via the H-phosphonate approach

Stereochemistry of Internucleotide Bond Formation by theH-Phosphonate Method. 5. The Role of Brønsted and H-Bonding Base Catalysis in RibonucleosideH-Phosphonate Condensation—Chemical and Stereochemical Consequences

Optimized Automated Solid Phase Synthesis of Oligonucleotides and Derivatives

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