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Synthesis of Nucleic Acid Fragments with 3′‐Deoxy‐3′‐ C ‐Methylenephosphonate Linkages − Oxidation Of Nucleoside 3′‐Deoxy‐3′‐ C ‐Methylenephosphinate Esters
Author(s) -
Winqvist Anna,
Strömberg Roger
Publication year - 2002
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/1099-0690(200209)2002:18<3140::aid-ejoc3140>3.0.co;2-x
Subject(s) - chemistry , pyridinium , pyridine , triethylamine , tautomer , nucleoside , nucleic acid , uridine , medicinal chemistry , hydrochloride , thymidine , iodine , stereochemistry , organic chemistry , rna , dna , biochemistry , gene
A study on the iodine oxidation of protected thymidine 5′‐(uridine 3′‐deoxy‐3′‐ C ‐methylenephosphinate) ( 1 ) to the corresponding thymidine 5′‐(uridine 3′‐deoxy‐3′‐ C ‐methylenephosphonate) ( 2 ) is reported. Oxidation with 80 m M iodine in pyridine/water (98:2, v/v) required 24 h for completion. The reaction is catalyzed by pyridinium ion as well as by triethylamine (TEA). The reactions appear to occur via the tricoordinate form of 1 : the anion in the TEA‐promoted reaction and the neutral tautomer for the acid (pyridinium ion) catalyzed reaction. Several sets of conditions are suggested for oxidation of oligo(nucleoside methylenephosphinate)s to the corresponding phosphonates. Solutions of 200 m M I 2 in pyridine/water, with either 1 M TEA or 1 M pyridine hydrochloride, gave half‐lives of less than 2 and 10 min, respectively. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)