Nucleoside 3′-N,N-Dialkylphosphonamidates as novel nucleotide units for the solution-phase oligonucleotide synthesis

Amides of Trivalent Phosphorus Acids as Phosphorylating Reagents for Proton-Donating Nucleophiles

“…Finally, phosphorylation of nucleosides by ATPA supplemented by hydrolysis, sulfohydrolysis, or acidolysis provides a pathway to prototropic systems of the hydrogenphosphonate (hydrophosphoryl) type. This method was used to prepare primary 343,[417][418][419][420][421][422][423][424] and secondary 349,394 nucleoside phosphites, phosphoramidites, 425 and phosphorothioites, 400,403,426 which are now widely used in various hydrophosphoryl and thiophosphoryl syntheses.…”

Reactions at Oxygen Atoms

“…The N(i-Prh analogs of216 can also be converted to 217 by simple hydrolysis with pyridinium chloride in pyridineIH 2 0 (98:2) [277]. Alternatively, treatment of 175 with salicyl chlorophosphite (218, a crystalline reagent) (to give 219) followed by hydrolysis (py/H 2 0) gives 217 (-90%) (Scheme 91) [276].…”

Development of a new synthetic method for oligodeoxynucleotides using 3′-H-phosphonamidate derivatives

“…In 1990, we reported a synthetic method using a nucleoside 3ʹ-N,N-diisopropylphosphonamidate as a monomer; however, the amino group was not a leaving group in the construction of an internucleotidic H-phosphonate diester linkage. 14,15 In this study, we developed a new synthetic method for ODNs using 3ʹ-H-phosphonamidate monomers bearing a heterocyclic amine as the leaving group. In this method, the H-phosphonate diester linkage was obtained from the H-phosphonamidate derivatives in only one step.…”