118149-27-2Relevant articles and documents
Synthesis of oligodeoxynucleoside phosphoromonothioates and phosphorodithioates by a phosphotriester method
Kehler, Jan,Pueschl, Ask,Dahl, Otto
, p. 1633 - 1636 (2007/10/03)
A phosphotriester method for the synthesis of dithymidine phosphoromonothioates and phosphorodithioates with new S-protecting groups has been investigated. Four of the S-protecting groups possesed catalytic activity, however side reactions occurred during deprotection. The best S- protecting group was 4-chloro-2-nitrobenzyl which could be removed with a minimum of side reactions (0.3 %). The coupling reagent PyFNOP (14) gave protected dithymidine phosphoromonothioate in 96 % yield after 15 rain coupling. Furthermore PyFNOP chemoselectively activates oxygen in nucleoside phosphorodithioate monomers 9 and can be used for the synthesis of oligodeoxynucleoside phosphorodithioates with mixed base sequences.
Solid phase synthesis of oligodeoxynucleoside phosphorodithioates by a phosphotriester method using a chemoselective coupling reagent
Kehler, Jan,Pueschl, Ask,Dahl, Otto
, p. 8041 - 8044 (2007/10/03)
A phosphotriester method has been developed for solid phase synthesis of oligodeoxynucleoside phosphorodithioates. Couplings are performed by chemoselective oxygen activation of protected nucleoside dithiophosphate anions 1, 7, 8, 9 with 4-nitro-6-trifluo
Synthesis of deoxydinucleoside phosphorodithioates
Brill, Wolfgang K.-D.,Nielsen, John,Caruthers, Marvin H.
, p. 3972 - 3980 (2007/10/02)
The synthesis of a new class of DNA analogues called phosphorodithioate DNA is described. This analogue, which has a deoxynucleoside-OPS2O-deoxynucleoside internucleotide linkage, is isosteric and isopolar with the normal phosphodiester, inert toward nucleases, and potentially useful for a large number of biochemical and biological applications. Two methods are described for synthesizing this derivative. One route begins by condensing a deoxynucleoside phosphorodiamidite with a second appropriately protected deoxynucleoside to yield a deoxydinucleoside phosphoramidite. Sulfhydrolysis with H2S generates the H-phosphonothioate, which upon oxidation with sulfur yields the deoxydinucleoside phosphorodithioate. Alternatively, sequential treatment of the deoxydinucleoside phosphoramidite with a mercaptan and sulfur yields the deoxydinucleoside phosphorodithioate triester. These deoxydinucleotides in protected form can then be used to introduce the dithioate internucleotide linkage into DNA. The second route for generating dithioate DNA uses deoxynucleoside phosphorothioamidites. Two derivatives, the deoxynucleoside 3′-N,N-dimetnyl- or 3′-(N,N-tetramethylenephosphorothioamidite), were found to be especially attractive synthons as they could be prepared in stable form via a one-flask synthesis procedure and used to form the deoxydinucleoside thiophosphite rapidly (1-2 min with tetrazole as activator) in high yield. Subsequent oxidation with sulfur generates the completely protected phosphorodithioate linkage.
