Sulfurization of H-Phosphonate Diesters by Elemental Sulfur under Aqueous Conditions



: Lönnberg Tuomas

Publisher: American Chemical Society

: 2017

: ACS Omega

: ACS OMEGA

: 2

: 8

: 5122

: 5127

: 6

: 2470-1343

DOI: https://doi.org/10.1021/acsomega.7b00970

: http://pubs.acs.org/doi/10.1021/acsomega.7b00970

: https://research.utu.fi/converis/portal/detail/Publication/27873577


To assess the plausibility of prebiotic nucleic acid polymerization by a sequential phosphitylation-sulfurization mechanism, the rates of hydrolysis and sulfurization of bis(2', 3'-O-methyleneadenosin-5'-yl)-H-phosphonate, a dinucleoside H-phosphonate diester, have been determined over a wide pH range (0.52-7.25) and in the presence of varying amounts (0-30 mg) of elemental sulfur. The pH-rate profile of hydrolysis resembled the one previously reported for the Hphosphonate analogue of thymidylyl-3', 5'-thymidine, with a relatively wide pH-independent region flanked by acid-and base-catalyzed regions. Sulfurization to the respective phosphorothioate diester, in turn, was found to be basecatalyzed over the entire pH range studied. Despite the facile hydrolysis of H-phosphonate diesters and the extremely low solubility of elemental sulfur in water, sulfurization and hydrolysis proceeded at comparable rates under neutral and mildly acidic conditions.

Last updated on 2024-26-11 at 21:55