TY - JOUR
T1 - Common and Potentially Prebiotic Origin for Precursors of Nucleotide Synthesis and Activation
AU - Fahrenbach, Albert C.
AU - Giurgiu, Constantin
AU - Tam, Chun Pong
AU - Li, Li
AU - Hongo, Yayoi
AU - Aono, Masashi
AU - Szostak, Jack W.
N1 - Funding Information:
J.W.S. is an Investigator of the Howard Hughes Medical Institute. This work was supported in part by grants from the Simons Foundation to J.W.S. (290363) and from the NSF (CHE-1607034) to J.W.S. A.C.F. is supported by a Research Fellowship from the Earth-Life Science Institute at the Tokyo Institute of Technology. L.L. is a Life Sciences Research Foundation Fellow. Part of this work was supported by JSPS KAKENHI Grant-in-Aid for Scientific Research on Innovative Areas "Hadean Bioscience", Grant Number JP26106003.
Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/7/5
Y1 - 2017/7/5
N2 - We have recently shown that 2-aminoimidazole is a superior nucleotide activating group for nonenzymatic RNA copying. Here we describe a prebiotic synthesis of 2-aminoimidazole that shares a common mechanistic pathway with that of 2-aminooxazole, a previously described key intermediate in prebiotic nucleotide synthesis. In the presence of glycolaldehyde, cyanamide, phosphate and ammonium ion, both 2-aminoimidazole and 2-aminooxazole are produced, with higher concentrations of ammonium ion and acidic pH favoring the former. Given a 1:1 mixture of 2-aminoimidazole and 2-aminooxazole, glyceraldehyde preferentially reacts and cyclizes with the latter, forming a mixture of pentose aminooxazolines, and leaving free 2-aminoimidazole available for nucleotide activation. The common synthetic origin of 2-aminoimidazole and 2-aminooxazole and their distinct reactivities are suggestive of a reaction network that could lead to both the synthesis of RNA monomers and to their subsequent chemical activation.
AB - We have recently shown that 2-aminoimidazole is a superior nucleotide activating group for nonenzymatic RNA copying. Here we describe a prebiotic synthesis of 2-aminoimidazole that shares a common mechanistic pathway with that of 2-aminooxazole, a previously described key intermediate in prebiotic nucleotide synthesis. In the presence of glycolaldehyde, cyanamide, phosphate and ammonium ion, both 2-aminoimidazole and 2-aminooxazole are produced, with higher concentrations of ammonium ion and acidic pH favoring the former. Given a 1:1 mixture of 2-aminoimidazole and 2-aminooxazole, glyceraldehyde preferentially reacts and cyclizes with the latter, forming a mixture of pentose aminooxazolines, and leaving free 2-aminoimidazole available for nucleotide activation. The common synthetic origin of 2-aminoimidazole and 2-aminooxazole and their distinct reactivities are suggestive of a reaction network that could lead to both the synthesis of RNA monomers and to their subsequent chemical activation.
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U2 - 10.1021/jacs.7b01562
DO - 10.1021/jacs.7b01562
M3 - Article
C2 - 28640999
AN - SCOPUS:85021993795
VL - 139
SP - 8780
EP - 8783
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 26
ER -