The Preparation of New Phosphorus-Centered Functional Groups for Modified Oligonucleotides and Other Natural Phosphates

Molecules

Arnaud Gautier²  Chrystel Lopin¹  Goulnara Garipova¹  Olivier Dubert¹  Irina Kalinina¹  Carmen Salcedo²  Sstien Balieu²  Stéphane Glatigny²  Jean-Yves Valnot²  Géraldine Gouhier² 

[1] id="af1-molecules-10-01048">Laboratoire des Fonctions Azotées et Oxygénées Complexes, UMR CNRS 6014, IRCOF-Université de Rouen, Rue Tesnières, F-76821 Mont Saint Aignan, Franc

关键词: Phosphate isoster;    difluorophosphonates;    difluoro-H-phosphinates;    nucleotide analogue;    cyclitol analogue;   

DOI  :  10.3390/10091048

来源: mdpi

【 摘 要 】

Efforts to develop synthetic methodologies allowing the preparation of α,α– difluorophosphonothioates, α,α–difluorophosphonodithioates, α,α–difluorophosphono- trithioates, and α,α–difluorophosphinates are reviewed in the light of applications in the field of modified oligonucleotides and cyclitol phosphates. Two successful approaches have been developed, based either on the addition of phosphorus-centered radicals onto gem–difluoroalkenes or on a process involving the addition of lithiodifluorophosphono- thioates 91 onto a ketone and the subsequent deoxygenation reaction of the adduct. The radical route successfully developed a practical route to α,α–difluoro–H–phosphinates which proved to be useful intermediates to a variety of phosphate isosters. The ionic route led to the first preparation of phosphonodifluoromethyl analogues of nucleoside– 3’–phosphates.

【 授权许可】

Unknown   
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