1053636-18-2Relevant academic research and scientific papers
Phosphorane intermediate vs. leaving group stabilization by intramolecular hydrogen bonding in the cleavage of trinucleoside monophosphates: Implications for understanding catalysis by the large ribozymes
Loennberg, Tuomas,Laine, Maarit
, p. 349 - 356 (2010)
Hydrolysis of 2′,3′-O-methyleneadenosin-5′-yl 5′-O-methyluridin-2′-yl 5′-O-methyl-2′- trifluoroacetamido-2′-deoxyuridin-3′-yl phosphate (1b) has been followed by HPLC over a wide pH range to study the effects of potential hydrogen bonding interactions of the 2′-trifluoroacetamido function on the rate and product distribution of the reaction. At pH -1 aqueous sodium hydroxide, no P-O5′ bond cleavage is observed. Compared to the 2′-OH counterpart 2, a modest rate enhancement is observed over the entire pH range studied. The absence of P-O5′ fission under alkaline conditions suggests hydrogen bond stabilization of the departing 3′-oxyanion by the neighboring 2′-trifluoroacetamido function.
Hydrolysis of 2′,3′-O-methyleneadenosin-5′-yl bis-5′-O-methyluridin-3′-yl phosphate: The 2′-hydroxy group stabilizes the phosphorane intermediate, not the departing 3′-oxyanion, by hydrogen bonding
Loennberg, Tuomas,Korhonen, Jonna
, p. 7752 - 7758 (2005)
Hydrolytic reactions of 2′,3′-O-methyleneadenosin-5′-yl bis-5′-O-methyluridin-3′-yl phosphate (1a) have been followed by RP HPLC over a wide pH range to elucidate the role of the 2′-OH group as an intermolecular hydrogen bond donor facilitating the cleavage of 1a. At pH a relatively wide range from pH 2 to 4, the hydrolysis is pH-independent and the P-O5′ bond is cleaved 1.6 times as rapidly as the P-O3′ bond. At pH 6, the reaction becomes first-order in hydroxide-ion concentration and cleavage of the P-O3′ bond starts to predominate, accounting for 89% of the overall hydrolysis in 10 mmol L-1 aqueous sodium hydroxide. Under alkaline conditions, the 2′-OH group facilitates the cleavage of 1 by a factor of 27 compared to the 2′-OMe counterpart, the influence on the P-O3′ and P-O5′ bond cleavage being equal. Accordingly, the 2′-hydroxy group stabilizes the phosphorane intermediate, not the departing 3′-oxyanion, by hydrogen bonding.
Hydrolytic stability of 2′,3′-O-methyleneadenos-5′-yl 2′,5′-di-O-methylurid-3′-yl 5′-O-methylurid- 3′(2′)-yl phosphate: Implications to feasibility of existence of phosphate-branched RNA under physiological conditions
Loennberg, Tuomas,Kiiski, Johanna,Mikkola, Satu
, p. 1089 - 1096 (2007/10/03)
Hydrolytic reactions of 2′,3′-O-methyleneadenos-5′-yl 2′,5′-di-O-methylurid-3′-yl 5′-O-methylurid- 3′(2′)-yl phosphate (1a,b) have been followed by RP-HPLC over a wide pH range to evaluate the feasibility of occurrence of phosphate-branched RNA under phys
