Synthesis and separation of diastereomers of O-(2,2,2-trifluoroethyl)-3′,5′-dinucleoside phosphates

Abstract

The synthesis, diastereomeric separation, and characterization are described for a series of novel O-(2,2,2-trifluoroethyl)-3′,5′-dinucleoside phosphates, required for incorporation into antisense probes in the magnetic resonance imaging investigation of biodistribution. Preliminary assignment of the absolute configuration of the Rp and Sp diastereomers is made on the basis of 31 P NMR spectra.

Determination of the Absolute Configuration of CN-Palladacycles by 31P{1H} NMR Spectroscopy Using (1R,2S,5R)-Menthyloxydiphenylphosphine as the Chiral Derivatizing Agent: Efficient Chirality Transfer in Phosphinite Adducts

“…Most of the publications in this area are based on the presumed shielding of the phosphorus atom by the aromatic group from the CDAs or on the sensitivity of 31 P­{ 1 H} NMR signals to the nature of the attached oxygen isotopes in the case of 16 O-, 17 O-, and 18 O-labeled phosphonate structures . There are only a few examples of the theoretical conformational analysis of these compounds, and only 1 H and 13 C­{ 1 H} NMR spectra were calculated for several phosphorus-containing compounds. ,, Thus, the empirical AC assignments are often presented as tentative assignments. ,,, With one exception, all of the mentioned CDAs used in the NMR-based protocols require their covalent bonding with the target molecules . The metal-containing reagents are of a fundamentally different type from organic CDAs due to their ability to achieve coordinative bonding with the substrate.…”