title: The preparation of new phosphorus-centered functional groups for modified oligonucleotides and other natural phosphates.
abstract: Efforts to develop synthetic methodologies allowing the preparation of alpha,alpha- difluorophosphonothioates, alpha,alpha-difluorophosphonodithioates, alpha,alpha-difluorophosphono- trithioates, and alpha,alpha-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 alpha,alpha-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.
authors.affiliation: Laboratoire des Fonctions Azotées et Oxygénées Complexes, IRCOF-Université de Rouen, Rue Tesnières, F-76821 Mont Saint Aignan, France.
authors.forename: Arnaud
authors.initials: A
authors.lastname: Gautier
authors.forename: Chrystel
authors.initials: C
authors.lastname: Lopin
authors.forename: Goulnara
authors.initials: G
authors.lastname: Garipova
authors.forename: Olivier
authors.initials: O
authors.lastname: Dubert
authors.forename: Irina
authors.initials: I
authors.lastname: Kalinina
authors.forename: Carmen
authors.initials: C
authors.lastname: Salcedo
authors.forename: Sébastien
authors.initials: S
authors.lastname: Balieu
authors.forename: Stéphane
authors.initials: S
authors.lastname: Glatigny
authors.forename: Jean-Yves
authors.initials: JY
authors.lastname: Valnot
authors.forename: Géraldine
authors.initials: G
authors.lastname: Gouhier
authors.forename: Serge R
authors.initials: SR
authors.lastname: Piettre
mesh_terms: D018360:Crystallography, X-Ray; D054812:Cyclitols / Q000737:chemistry; D007477:Ions; D008958:Models, Molecular; D009841:Oligonucleotides / Q000737:chemistry*; D010710:Phosphates / Q000737:chemistry*; D010758:Phosphorus / Q000737:chemistry*
chemical_list: D054812:Cyclitols; D007477:Ions; D009841:Oligonucleotides; D010710:Phosphates; D010758:Phosphorus