The preparation of new phosphorus-centered functional groups for modified oligonucleotides and other natural phosphates.
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.
Gautier
Arnaud
A
Laboratoire des Fonctions Azotées et Oxygénées Complexes, IRCOF-Université de Rouen, Rue Tesnières, F-76821 Mont Saint Aignan, France.
Lopin
Chrystel
C
Garipova
Goulnara
G
Dubert
Olivier
O
Kalinina
Irina
I
Salcedo
Carmen
C
Balieu
Sébastien
S
Glatigny
Stéphane
S
Valnot
Jean-Yves
JY
Gouhier
Géraldine
G
Piettre
Serge R
SR
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*
D054812:Cyclitols; D007477:Ions; D009841:Oligonucleotides; D010710:Phosphates; D010758:Phosphorus