Unknown

Dataset Information

0

Studies toward the oxidative and reductive activation of C-S bonds in 2'-S-aryl-2'-thiouridine derivatives.


ABSTRACT: Studies directed toward the oxidative and reductive desulfurization of readily available 2'-S-aryl-2'-thiouridine derivatives were investigated with the prospect to functionalize the C2'-position of nucleosides. The oxidative desulfurization-difluorination strategy was successful on 2-(arylthio)alkanoate surrogates, while extension of the combination of oxidants and fluoride sources was not an efficient fluorination protocol when applied to 2'-S-aryl-2'-thiouridine derivatives, resulting mainly in C5-halogenation of the pyrimidine ring and C2'-monofluorination without desulfurization. Cyclic voltammetry of 2'-arylsulfonyl-2'-deoxyuridines and their 2'-fluorinated analogues showed that cleavage of the arylsulfone moiety could occur, although at relatively high cathodic potentials. While reductive-desulfonylation of 2'-arylsulfonyl-2'-deoxyuridines with organic electron donors (OEDs) gave predominantly base-induced furan type products, chemical (OED) and electrochemical reductive-desulfonylation of the ?-fluorosulfone derivatives yielded the 2'-deoxy-2'-fluorouridine and 2',3'-didehydro-2',3'-dideoxy-2'-fluorouridine derivatives. These results provided good evidence of the generation of a C2'-anion through carbon-sulfur bond cleavage, opening new horizons for the reductive-functionalization approaches in nucleosides.

SUBMITTER: Rayala R 

PROVIDER: S-EPMC4806340 | BioStudies | 2016-01-01

REPOSITORIES: biostudies

Similar Datasets

2016-01-01 | S-EPMC4984408 | BioStudies
2006-01-01 | S-EPMC2532670 | BioStudies
2000-01-01 | S-EPMC1221366 | BioStudies
2020-01-01 | S-EPMC7465190 | BioStudies
2019-01-01 | S-EPMC6457195 | BioStudies
2019-01-01 | S-EPMC6526958 | BioStudies
2017-01-01 | S-EPMC5514717 | BioStudies
1000-01-01 | S-EPMC6151833 | BioStudies
2010-01-01 | S-EPMC2857653 | BioStudies
2016-01-01 | S-EPMC4931866 | BioStudies