Prebiotic Phosphorylation and Concomitant Oligomerization of Deoxynucleosides to form DNA

Angew Chem Int Ed Engl. 2021 May 3;60(19):10775-10783. doi: 10.1002/anie.202015910. Epub 2021 Mar 30.

Abstract

Recent demonstrations of RNA-DNA chimeras (RDNA) enabling RNA and DNA replication, coupled with prebiotic co-synthesis of deoxyribo- and ribo-nucleotides, have resurrected the hypothesis of co-emergence of RNA and DNA. As further support, we show that diamidophosphate (DAP) with 2-aminoimidazole (amido)phosphorylates and oligomerizes deoxynucleosides to form DNA-under conditions similar to those of ribonucleosides. The pyrimidine deoxynucleoside 5'-O-amidophosphates are formed in good (≈60 %) yields. Intriguingly, the presence of pyrimidine deoxynucleos(t)ides increased the yields of purine deoxynucleotides (≈20 %). Concomitantly, oligomerization (≈18-31 %) is observed with predominantly 3',5'-phosphodiester DNA linkages, and some (<5 %) pyrophosphates. Combined with previous observations of DAP-mediated chemistries and the constructive role of RDNA chimeras, the results reported here help set the stage for systematic investigation of a systems chemistry approach of RNA-DNA coevolution.

Keywords: DNA; RNA; diamidophosphate; oligomerization; phosphorylation.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • DNA / chemistry*
  • Molecular Structure
  • Nucleotidases / chemical synthesis*
  • Nucleotidases / chemistry
  • Phosphorylation

Substances

  • DNA
  • Nucleotidases
  • deoxynucleotidase