79670-88-5Relevant academic research and scientific papers
Synthesis of Nucleoside Triphosphates from 2′-3′-Protected Nucleosides Using Trimetaphosphate
Mohamady, Samy,Taylor, Scott D.
, p. 580 - 583 (2016)
Chemists have been attempting to triphosphorylate nucleosides and other alcohols using trimetaphosphate (TriMP) since the 1960s. However, this route appears to have been abandoned due to poor yields. The first practical syntheses of nucleoside triphosphates (NTPs) are reported using TriMP as the key reagent. This was achieved by reacting the tetrabutylammonium salt of TriMP with mesitylenesulfonyl chloride in the presence of DABCO in pyridine followed by the addition of an appropriately protected nucleoside and phthalimide. Quenching the reaction with aqueous buffer followed by hydrolysis of the OH protecting groups gave the NTPs in good yield.
A P(V)-N activation strategy for the synthesis of nucleoside polyphosphates
Sun, Qi,Gong, Shanshan,Sun, Jian,Liu, Si,Xiao, Qiang,Pu, Shouzhi
, p. 8417 - 8426 (2013/09/24)
A general and high-yielding synthesis of nucleoside 5′-triphosphates (NTPs) and nucleoside 5′-diphosphates (NDPs) from protected nucleoside 5′-phosphoropiperidates promoted by 4,5-dicyanoimidazole (DCI) has been developed. 31P NMR tracing experiments showed that the sequential deprotection and coupling reactions were exceptionally clean. The phosphoropiperidate exhibited superior reactivity to the conventional phosphoromorpholidate toward DCI-promoted NTP/NDP synthesis. The experimental results suggested that the mechanism of DCI activation could be distinctive for NTP and NDP synthesis, depending on the different nucleophilicity of pyrophosphate and phosphate.
New photoactivated protecting groups. 6. p-Hydroxyphenacyl: A phototrigger for chemical and biochemical probes
Park, Chan-Ho,Givens, Richard S.
, p. 2453 - 2463 (2007/10/03)
p-Hydroxyphenacyl, a new photoactive, aqueous soluble protecting group is proposed as a second generation α-keto 'cage' reagent, a phototrigger for the efficient, rapid release of bioactive phosphates, e.g., inorganic phosphate (P(i)) and ATP (Givens, R.S.; Park, C.-H. Tetrahedron Lett. 1996, 37, 6259-6262). p-Hydroxyphenacyl esters 6c and 7 trigger the release of P(i) and ATP when irradiated at wavelengths between 300-350 nm also yielding p-hydroxyphenylacetic acid (8) from the rearrangement of the intermediate α-keto carbocation or its equivalent. In contrast, unsubstituted and m-substituted phenacyl esters yield only photoreduction and radical coupling products and none of the rearrangement product. Quantum efficiencies of 0.38 ± 0.04 were measured for the disappearance of the p-hydroxyphenacyl phosphate esters 6c and 7; the appearance efficiencies for 8 and ATP were 0.30 ± 0.03. Rates of release of ~107 s-1 or better are observed for these esters with only minor variations in efficiencies and rate constants between these two examples of the p-hydroxyphenacyl phototrigger. Just as was found for the desyl 'cage' series reported earlier (Givens, R.S.; Athey, P.S.; Kueper, L.W., III; Matuszewski, B.; Xue, J.-y.; Fister, T.J. Am. Chem. Soc. 1993, 115, 6001-6010), the p-hydroxyphenacyl derivatives react via their triplet states. Amino substituents, i.e., p-amino-, p-acetamido-, and p-(carbomethoxyamino)phenacyl phosphates 6f-h, were also investigated, but these analogues proved to be inferior as phototriggers when compared with p-hydroxyphenacyl.
