Angewandte Chemie International Edition
10.1002/anie.201903400
COMMUNICATION
nucleosides 12 are possible, summing up to a total of four epimers. progenitors are ruled out because of their inability to polymerize
or their stereochemical variability. With the DApiNA nucleosides
These results not only prove the highly selective formation of -
12, a potential DNA nucleoside progenitor was found. Likewise,
deoxynucleosides by activation of acetaldehyde and an in-situ
sugar-forming cascade (Figure 3), but also in particular the
stereochemical course, which has led to the preferred formation
of deoxyribose over other deoxysugars. The molecular
evolutionary selection principle is clearly the minimization of
possible stereoisomers. This corresponds to a minimization of
entropy and, by definition, to a shift from equilibrium, which can
be understood as a criterion for Life on a molecular basis.
this DApiNA nucleoside 12 could not persist. This proves the
ingenuity of Nature to minimize the number of possible
stereoisomers (Supplementary Table S8). This work explains why
D-deoxyribose is favored over all other sugars and thus opens a
non-enzymatic pathway towards DNA nucleosides 3. We
therefore conclude that the DNA world did evolve much earlier
than previously proposed.
The RNA world hypothesis is the central consensus in the origins
of life research, although many questions arising from this
hypothesis have not yet been answered. Among these are the
transition from RNA to DNA and the pre-eminence of D-ribose in
all coding polymers of life. Our results finally provide a rational
and provable mechanism for the formation of DNA nucleosides 3.
In a nucleobase activated aldol reaction, a transition from all
canonical nucleobases 1a-d, via the vinyl nucleobase
intermediates 8a-d, to deoxyribonucleosides 3a-d occurs. The
reaction proceeds under constant, ambient conditions, in water,
basic mineral additives enhance the reaction. When using
glycolaldehyde 13, formaldehyde 15 or dihydroxyacetone 11,
instead of glyceraldehyde 7, deoxynucleoside derivatives were
also detected. However, these potential DNA nucleoside
Acknowledgements
We acknowledge financial support from the Ludwig-Maximilians-
University Munich, the Deutsche Forschungsgemeinschaft DFG
(
INST 86/1807-1 FUGG, SFB 235, the Cluster of Excellence
ORIGINS), and the Max-Planck-Society (Max-Planck-Fellow
Research Group Origins of Life).
Keywords: DNA progenitor • deoxyribonucleoside •
deoxyapinonucleoside • origin of Life • prebiotic chemistry
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