A simple one-step synthesis of ribonucleoside 2′,3′-cyclic phosphate 5′-phosphates

Simoncsits, András; Tomasz, J.

doi:10.1016/0005-2787(75)90235-x

Cited by 10 publications

(4 citation statements)

References 15 publications

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“…To develop a unified and reliable approach to incorporate these analogues we exploited an enzymatic route using 3‘,5‘-bisphosphorylated derivatives and T 4 RNA ligase. , We chose uridine analogues to develop a representative incorporation strategy. Difluoromethyluridine 3‘,5‘-bisphosphate 21 (Scheme ) was synthesized from uridine 7 using a slightly modified version of the method described by Barrio et al Reactions were conducted at room temperature instead of −10 to −15 °C to compensate for the lower reactivity of uridine analogues toward phosphorylation . The reaction mixture was purified by ion-exchange chromatography on a DEAE−cellulose column, eluting with a linear gradient of 0.15−0.5 M triethylammonium bicarbonate (TEAB, pH 8.0).…”

Section: Resultsmentioning

confidence: 99%

Synthesis of 2‘-C-Difluoromethylribonucleosides and Their Enzymatic Incorporation into Oligonucleotides

Liao

Piccirilli

2005

J. Org. Chem.

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[Chemical reaction: See text] Nucleosides bearing a branched ribose have significant promise as therapeutic agents and biotechnological and biochemical tools. Here we describe synthetic entry into a new subclass of these analogues, 2'-C-beta-difluoromethylribonucleosides. We constructed the glycosylating agent 4 in three steps from 1,3,5-tri-O-benzoyl-alpha-D-ribofuranose 1. The key steps included nucleophilic addition of difluoromethyl phenyl sulfone to 2-ketoribose 2 followed by mild and efficient reductive desulfonation. Ribofuranose 4 glycosylated bis(trimethylsilyl)uracil directly, giving difluoromethyluridine 7 efficiently after deprotection. Conversion of 4 to the corresponding ribofuranosyl bromide allowed efficient access to C, A, and G analogues. A related approach starting from methyl D-ribofuranose offered synthetic entry into the diastereomeric manifold, 2'-C-alpha-difluoromethyl-arabino-alpha-pyrimidine. To incorporate 2'-C-beta-difluoromethyluridine into an oligodeoxynucleotide we converted 7 to the bisphosphate and carried out successive ligation reactions using T4 RNA ligase and T4 DNA ligase. Analogous to natural RNA linkages, the resulting oligonucleotide undergoes hydroxide-catalyzed backbone scission at the difluoromethyluridine residue via internal transphosphorylation.

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Section: Resultsmentioning

confidence: 99%

Synthesis of 2‘-C-Difluoromethylribonucleosides and Their Enzymatic Incorporation into Oligonucleotides

Liao

Piccirilli

2005

J. Org. Chem.

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“…Similarly, reaction of unprotected nucleosides (A, C, G, U) with pyrophosphoryl chloride followed by buffered hydrolysis (pH = 7) results in the formation of cyclic‐2′,3′‐phosphonucleoside‐5′‐phosphates (Fig. ; Simoncsits and Tomasz, ). This reaction is successful for adenosine, cytidine, and guanosine.…”

Section: Cyclic Nucleoside Phosphates and Phosphorothioatesmentioning

confidence: 99%

Overview of the Synthesis of Nucleoside Phosphates and Polyphosphates

Johnson

Widlanski

2003

CP Nucleic Acid Chemistry

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This overview summarizes methodology used for the synthesis of nucleoside mono-, di-, and triphosphates. Selected techniques such as the Mitsunobu reaction, displacement reactions involving nucleoside 5'-tosylates, "anion-exchange" techniques, and phosphoramidite and phosphoramidate methodologies are highlighted. The chemistry of phosphorylation is detailed with respect to advantages and limitations under various conditions. Applicability of the methods toward the synthesis of analogs such as imidophosphates, phosphorothioates, and radiolabeled nucleotides is also addressed.

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“…Two subsequent filtrations, first through a Dowex 50 W x 4 (H' ), then through a Dowex 2 x 8 (-OH) column, removed the protecting ketal group and afforded propionyl-dethia(carba)pantetheine 18 in 50% yield (based on 16). Phosphorylation of 19 was camed out withcyanoethylphosphate in analogy to the procedure of Stewart and Wieland (1) (9). Compound 11 was first described by Moffat and Khorana (5).…”

Section: Synthesis Of Propionyl-dethia(carba)-coenzyme A(1)mentioning

confidence: 99%

Synthesis, characterization, and enzymic conversion of nonhydrolysable analogues of propionylcoenzyme A

Zhao¹,

Michenfelder²,

Rétey³

1994

Can. J. Chem.

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We describe the synthesis of three novel analogues of propionyl-coenzyme A, in which the sulfur atom has been replaced by methylene, ethylene, and thiomethylene, respectively. All three analogues, propion I dethia(carba)-CoA (I), propionyl-dethia-(dicarba)-CoA (2), and S-(2-oxobutany1)-CoA (3) were characterized by I H and '6-NMR spectroscopy and FAB mars spectrometry. Propionyl-CoA-oxaloacetate transcarboxylase from Propionibacteriunl sherrnanii accepted the novel analogues as substrates and carboxylated them to the corresponding methylmalonyl-CoA analogues (4-6). The latter were further converted into the succinyl-CoA analogues by the coenzyme-BIZ-dependent methylmalonyl-CoA mutase from the same organism. The succinyl-CoA analogues, succinyl-dethia(carba)-CoA (7), succinyl-dethia(dicarba)-CoA (S), and 4-carboxy(2-oxobutany1)-CoA (9) were obtained on a preparative scale and their Michaelis constants (K,) with methylmalonyl-CoA mutase were determined to be 0.136,2.20, and 0.132 mM, respectively (K, for succinyl-CoA is 0.025 mM). The V, , , values for 7,8, and 9 are I. I, 0.013, and 0.0047 pmol min-I U-l, respectively (V,,, for succinyl CoA is 1.0). The utility of the novel coenzyme A analogues in enzyme mechanistic studies is discussed.Y m ZHAO, MARTINA MICHENFELDER, et Jhos M~Y . Can. J. Chem. 72, 164 (1994). On dCcrit la synthkse de trois nouveaux analogues du propionyl-coenzyme-A dans lesquels l'atome de soufre a Ct C remplacC respectivement par un mkthylkne, un Cthylkne et un thiomCthylkne. On a caractCrisC les trois analogues, le propionyldCthia(carba)-CoA (I), le propionyl-dCthia(dicarba)-CoA (2) et le S-(2-oxo-butany1)-CoA (3) par spectroscopie RMN du 'H et du "P et par spectromCtrie de masse FAB. La propionyl-CoA-oxaloacCtate transcarboxylase du Propionibacterium shermar~ii accepte les nouveaux analogues comme substrats et par carboxylation les transforme en analogues mCthylmalony1-CoA correspondants (4-6). Par la suite, on a transform6 ces derniers en analogues succinyl-CoA en les soumettant k la mtthylmalonyl-CoA mutase dkpendante du c~e n z y m e -B~~ provenant du m&me organisme. On a obtenu les analogues succinyl-CoA, succinyl-dCthia(carba)-CoA (7), succinyl-dCthia(dicarba)-CoA (8) [Traduit par la ridaction]

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A simple one-step synthesis of ribonucleoside 2′,3′-cyclic phosphate 5′-phosphates

Cited by 10 publications

References 15 publications

Synthesis of 2‘-C-Difluoromethylribonucleosides and Their Enzymatic Incorporation into Oligonucleotides

Synthesis of 2‘-C-Difluoromethylribonucleosides and Their Enzymatic Incorporation into Oligonucleotides

Overview of the Synthesis of Nucleoside Phosphates and Polyphosphates

Synthesis, characterization, and enzymic conversion of nonhydrolysable analogues of propionylcoenzyme A

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