Phosphorylation of Nucleosides with Phosphorus Oxychloride in Trialkyl Phosphate.

Ikemoto, Tomomi; Haze, Akira; Hatano, Hiroyuki; Kitamoto, Yoshifumi; Ishida, Masato; Nara, Kiyoshi

doi:10.1248/cpb.43.210

Cited by 42 publications

(40 citation statements)

References 2 publications

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“…Phosphorylation of L-nucleosides L-nucleosides of adenine and uracil were phosphorylated at the 5′-position (Ikemoto et al 1995). A mixture of L-nucleoside (30 mmol) and water (15 mmol) in TEP (1.0 mL) was treated with POCl 3 (60 mmol) at 0°C for 5 h (L-adenosine) or 25 h (L-uridine).…”

Section: Methodsmentioning

confidence: 99%

Homochiral Selectivity in RNA Synthesis: Montmorillonite-catalyzed Quaternary Reactions of D, L-Purine with D, L- Pyrimidine Nucleotides

Joshi

Aldersley

Ferris

2010

Orig Life Evol Biosph

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Selective adsorption of D, L-ImpA with D, L-ImpU on the platelets of montmorillonite demonstrates an important reaction pathway for the origin of homochirality in RNA synthesis. Our earlier studies have shown that the individual reactions of D, L-ImpA or D, L-ImpU on montmorillonite catalyst produced oligomers which were only partially inhibited by the incorporation of both D- and L-enantiomers. Homochirality in these reactions was largely due to the formation of cyclic dimers that cannot elongate. We investigated the quaternary reactions of D, L-ImpA with D, L-ImpU on montmorillonite. The chain length of these oligomers increased from 9-mer to 11-mer as observed by HPLC, with a concomitant increase in the yield of linear dimers and higher oligomers in the reactions involving D, L-ImpA with D, L-ImpU as compared to the similar reactions carried out with D-enantiomers only. The formation of cyclic dimers of U was completely inhibited in the quaternary reactions. The yield of cyclic dimers of A was reduced from 60% to 10% within the dimer fraction. 12 linear dimers and 3 cyclic dimers were isolated and characterized from the quaternary reaction. The homochirality and regioselectivity of dimers were 64.1% and 71.7%, respectively. Their sequence selectivity was shown by the formation of purine-pyrimidine (54-59%) linkages, followed by purine-purine (29-32%) linkages and pyrimidine-pyrimidine (9-13%) linkages. Of the 16 trimers detected, 10 were homochiral with an overall homochirality of 73-76%. In view of the greater homochirality, sequence- and regio- selectivity, the quaternary reactions on montmorillonite demonstrate an unexpectedly favorable route for the prebiotic synthesis of homochiral RNA compared with the separate reactions of enantiomeric activated mononucleotides.

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Section: Methodsmentioning

confidence: 99%

Homochiral Selectivity in RNA Synthesis: Montmorillonite-catalyzed Quaternary Reactions of D, L-Purine with D, L- Pyrimidine Nucleotides

Joshi

Aldersley

Ferris

2010

Orig Life Evol Biosph

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“…29 This is probably due to the reason that, under acidic conditions, a 2′-deoxy-nucleoside may form a more stable oxonium intermediate at the ribosyl C-1′ position, thus facilitating a rapid hydrolysis. Because of the lack of acid stability, phosphorylation of 20 using the conventional POCl 3 /TEP method 30 is problematic, because this method requires an aqueous workup, which will result in an acidic solution. It was indeed found that the 8-substituted 2′-deoxy-AMP that formed in the phosphorylation reaction degraded rapidly during the aqueous workup (data not shown).…”

Section: Chemistrymentioning

confidence: 99%

2′-Deoxy Cyclic Adenosine 5′-Diphosphate Ribose Derivatives: Importance of the 2′-Hydroxyl Motif for the Antagonistic Activity of 8-Substituted cADPR Derivatives

et al. 2008

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The structural features needed for antagonism at the cyclic ADP-ribose (cADPR) receptor are unclear. Chemoenzymatic syntheses of novel 8-substituted 2′-deoxy-cADPR analogues, including 8-bromo-2′-deoxycADPR 7, 8-amino-2′-deoxy-cADPR 8, 8-O-methyl-2′-deoxy-cADPR 9, 8-phenyl-2′-deoxy-cADPR 10 and its ribose counterpart 8-phenyl-cADPR 5 are reported, including improved syntheses of established antagonists 8-amino-cADPR 2 and 8-bromo-cADPR 3. Aplysia californica ADP-ribosyl cyclase tolerates even the bulky 8-phenyl-nicotinamide adenine 5′-dinucleotide as a substrate. Structure-activity relationships of 8-substituted cADPR analogues in both Jurkat T-lymphocytes and sea urchin egg homogenate (SUH) were investigated. 2′-OH Deletion decreased antagonistic activity (at least for the 8-amino series), showing it to be an important motif. Some 8-substituted 2′-deoxy analogues showed agonist activity at higher concentrations, among which 8-bromo-2′-deoxy-cADPR 7 was, unexpectedly, a weak but almost full agonist in SUH and was membranepermeant in whole eggs. Classical antagonists 2 and 3 also showed previously unobserved agonist activity at higher concentrations in both systems. The 2′-OH group, without effect on the Ca 2+

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“…The selective phosphorylation of uridine has proven to be particularly difficult using Yoshikawa's procedure, 10 which may be due to the highest occupied molecular orbital energy of uracil. 17 One of the chief concerns in any fluidic experiment is the formation of solids in the reactor. Thus, a significant challenge of converting batch conditions into a flow process is the poor solubility of nucleosides in common organic solvents.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Fully Automated Continuous Meso-flow Synthesis of 5′-Nucleotides and Deoxynucleotides

Zhu

Tang

Cao

et al. 2014

Org. Process Res. Dev.

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The first continuous meso-flow synthesis of natural and non-natural 5′-nucleotides and deoxynucleotides is described, representing a significant advance over the corresponding in-flask method. By means of this mesoflow technique, a synthesis with time consumption and high-energy consumption becomes facile to generate products with great efficiency. An abbreviated duration, satisfactory output, and mild reaction conditions are expected to be realized under the present procedure.

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Phosphorylation of Nucleosides with Phosphorus Oxychloride in Trialkyl Phosphate.

Cited by 42 publications

References 2 publications

Homochiral Selectivity in RNA Synthesis: Montmorillonite-catalyzed Quaternary Reactions of D, L-Purine with D, L- Pyrimidine Nucleotides

Homochiral Selectivity in RNA Synthesis: Montmorillonite-catalyzed Quaternary Reactions of D, L-Purine with D, L- Pyrimidine Nucleotides

2′-Deoxy Cyclic Adenosine 5′-Diphosphate Ribose Derivatives: Importance of the 2′-Hydroxyl Motif for the Antagonistic Activity of 8-Substituted cADPR Derivatives

Fully Automated Continuous Meso-flow Synthesis of 5′-Nucleotides and Deoxynucleotides

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