5983-11-9Relevant articles and documents
Electrophile-promoted addition of hydroxymethylphosphonate to 4′,5′-didehydronucleosides: a way to novel isosteric analogues of 5′-nucleotides
To?ík, Zdeněk,Dvo?áková, Ivana,Liboska, Radek,Budě?ínsky, Milo?,Masojídková, Milena,Rosenberg, Ivan
, p. 4516 - 4534 (2008/02/01)
An electrophile-promoted addition of dialkyl-hydroxymethylphosphonate to the protected 4′,5′-didehydronucleosides resulted in an epimeric mixture of 4′-dialkylphosphonomethoxy derivatives of 2′,5′-dideoxynucleosides, novel analogues of 2′-deoxynucleoside 5′-monophosphates. Several types of electrophiles (pyridinium tosylate, NIS, NBS, MCPBA and others) were evaluated in addition reactions with 4′,5′-didehydrothymidine. Out of them, pyridinium tosylate was found to have a practical usefulness in these transformations. Its use has led to the preparation of a series of 4′-phosphonomethoxy derivatives of common 2′-deoxynucleosides. On biological screening, these free phosphonic acids exerted no significant cytostatic or antiviral activity.
Nucleoside Sultones: Synthons for the Preparation of Novel Nucleotide Analogues. 1. Synthesis and Ring-Opening Reactions
Crooks, Peter A.,Reynolds, Robert C.,Maddry, Joseph A.,Rathore, Anita,Akhtar, M. Shamim,et al.
, p. 2830 - 2835 (2007/10/02)
Treatment of either the 5'-O-tosyl or the 5'-O-mesyl derivative of 3'-O-mesylthymidine with lithium acetylide-ethylenediamine complex in DMSO affords the intramolecular 6,3-ester of 1,2,5,6-tetradeoxy-1-(3,4-dihydro-5-methyl-2,4-dioxo-1(2H)-pyrimidinyl)-β-D-erythro-hexofuranuronosulfonic acid (2).Similarly, the 5'-O-tosyl or 5'-O-mesyl derivative of 1-(2-deoxy-3-O-mesyl-β-D-threo-pentofuranosyl)thymine affords the intramolecular 6,3-ester of 1,2,5,6-tetradeoxy-1-(3,4-dihydro-5-methyl-2,4-dioxo-1(2H)-pyrimidinyl)-β-D-threo-hexofuranuronosulfonic acid (5).Sultone 5 reacts with a variety of nucleophiles to afford good yields of the corresponding 3'-substituted sulfonate salts (6, 7, 9, and 10) and, in some cases, the unsaturated nucleoside 8.Sultone 2 was generally much less susceptible to ring opening by nucleophiles.However, in the presence of base, nucleophilic substitution with azide ion did proceed via the intermediate anhydronucleoside, 11, to afford 6.Reaction of 2 with EtOH-NaOH afforded a 1:1 mixture of the epimeric 3'-hydroxy compounds 9 and 12.The above sulfonate salts represent interesting new isosteres of nucleoside 5'-O-phosphates.