7150-62-1Relevant articles and documents
Noncanonical RNA Nucleosides as Molecular Fossils of an Early Earth—Generation by Prebiotic Methylations and Carbamoylations
Schneider, Christina,Becker, Sidney,Okamura, Hidenori,Crisp, Antony,Amatov, Tynchtyk,Stadlmeier, Michael,Carell, Thomas
supporting information, p. 5943 - 5946 (2018/04/30)
The RNA-world hypothesis assumes that life on Earth started with small RNA molecules that catalyzed their own formation. Vital to this hypothesis is the need for prebiotic routes towards RNA. Contemporary RNA, however, is not only constructed from the four canonical nucleobases (A, C, G, and U), it also contains many chemically modified (noncanonical) bases. A still open question is whether these noncanonical bases were formed in parallel to the canonical bases (chemical origin) or later, when life demanded higher functional diversity (biological origin). Here we show that isocyanates in combination with sodium nitrite establish methylating and carbamoylating reactivity compatible with early Earth conditions. These reactions lead to the formation of methylated and amino acid modified nucleosides that are still extant. Our data provide a plausible scenario for the chemical origin of certain noncanonical bases, which suggests that they are fossils of an early Earth.
NH-Acidities of Some Sterically Hindered Ureas
Pojarlieff, Ivan G.,Blagoeva, Iva B.,Kirby, Anthony J.,Mikhova, Bozhana P.,Atay, Ergun
, p. 220 - 221 (2007/10/03)
Introduction of an N-methyl group in to ethyl N-methylhydantoate causes a fourfold decrease in the rate of base-catalysed exchange of the N-H proton; a second methyl group restores the rate to close to that of the N-unsubstituted hydantoate; the latter ef
BASE CATALYZED CYCLIZATION OF SUBSTITUTED ESTERS OF HYDANTOIC AND THIOHYDANTOIC ACID
Kavalek, Jaromir,Machacek, Vladimir,Svobodova, Gabriela,Sterba, Vojeslav
, p. 375 - 390 (2007/10/02)
Base catalyzed cyclization rates have been measured of 22 derivatives of hydantoic and thiohydantoic acid esters in water and methanol.The cyclization of methyl and ethyl esters of hydantoic and 5-methylhydantoic acids is accompanied by hydrolysis of the ester group, whereas with the other derivatives the hydrolysis does not take place.Hydrolysis of the cyclization products (hydantoin and thiohydantoin derivatives) is not significant under the kinetic conditions.The cyclization of methyl ester of 5-phenylhydantoic acid in methanol is reversible; the equilibrium mixture contains 30percent of the starting ester.In all the cases the cyclization is subject to specific base catalysis; exceptions are esters of 5-phenylthiohydantoic and 5-phenyl-2-methylthiohydantoic acids whose cyclizations are subject to general base catalysis.Substituents always accelerate the cyclization.The 3-substituents have the greatest effects, the cyclization rate being considerably increased with bulk of the substituents; similarly large effect of 5-phenyl group consists mainly in its polar effects on the pre-equilibrium.The cyclizations are slower in methanol at the same concentration of the lyate ion: the greatest difference (up to 3 orders of magnitude) is observed with the 5-phenyl derivatives.