Improved methods for h-phosphonate synthesis of mono- and...

C - Chemistry – Metallurgy – 07 – H

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C07H 19/10 (2006.01) C07H 19/20 (2006.01) C07H 21/00 (2006.01)

Patent

CA 2205218

New methods of synthesizing mono- and oligo- nucleotide H-phosphonates are disclosed. The methods comprise contacting a mononucleoside with phosphonic acid and benzoyl anhydride or propane phosphonic acid anhydride to yield the corresponding mononucleoside H-phosphonate. Preferably a catalytic amount of triphosgene is also used. A similar procedure can be used to couple a first mononucleoside to a second mononucleoside or to an oligonucleotide, the method comprising contacting, in the presence of benzoic anhydride or propane phosphonic acid anhydride and, preferably, when benzoic anhydride is used, a catalytic amount of triphosgene, a mononucleotide or oligonucleotide having a free 5' hydroxyl with a mononucleoside having a 3' hydroxyl-bearing phosphorous moiety (preferably H-phosphonate).

Nouvelles méthodes de synthèse de H-phosphonates de mono- et d'oligonucléotides. Ces méthodes consistent à mettre en contact un mononucléoside avec de l'acide phosphonique et de l'anhydride benzoylique ou un anhydre d'acide propanephosphonique de façon à obtenir le H-phosphonate de mononucléoside. On privilégie également l'emploi d'une certaine quantité de triphosgène catalytique. Un procédé semblable peut être utilisé pour combiner un premier mononucléoside avec un second mononucléoside ou avec un oligonucléotide; le procédé consiste à mettre en contact, en présence d'anhydride benzoïque ou d'anhydride d'acide propanephosphonique et, de préférence d'une quantité catalytique de triphosgène lorsque c'est l'anhydride benzoïque qui est utilisé, un mononucléotide ou un oligonucléotide renfermant un hydroxyle libre en 5' avec un mononucléoside renfermant une fraction phosphoreuse hydroxylée en 3' (de préférence du H-phosphonate).

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