Aminonucleosides and their derivatives. IV^ISynthesis of the 3′-amino-3′-deoxynucleoside 5′-phosphates

Abstract

A new procedure has been developed for the synthesis of 3'-amino-3'-deoxyribonucleosides of adenine, cytosine and uracil by condensing the trimethylsilylated bases with peracylated 3-azido-3-deoxyribose derivative. The azido group could subsequently be reduced to amino. The 5'-phosphates of these nucleosides have been prepared and the analogues have been tested for their ability to stimulate the ribosome-catalyzed reaction of 3'(2')-O-(N-formylmethionyl) adenosine 5'-phosphate with phenylalanyl-tRNA.

Properties of 2′,3′‐dideoxy‐2′,3′‐dehydrothymidine 5′‐triphosphate in terminating DNA synthesis catalyzed by several different DNA polymerases

“…The 17-member oligonucleotide d(GTAAAACCACGGCCAGT) and the 14-member d(CCCAGTCACGACGT) were labeled with [32p] at the 5'-position using polynucleotide kinase and [7-32p]ATP. dNTP(3'-NH2) and dNTP(3'-N3) [10], dNTP(3'-F) Jill dNTP(3'-OCH3) [12], araNTP(3'-N3) and ara-NTP(3'-NH2) [13] were synthesized as described.…”

Inhibition of reverse transcription in rat liver intracisternal A‐particles by thymidine derivatives

“…dTTP(3'N3) and araTTP(3'Ns) were synthesized by triphosphorylation of 3 ' -azido-2' ,3 ' -dideoxythymidine [15] and araAzT [16] using established methods [17,18].…”

Nucleotides. Part LVII.. Synthesis of phosphoramidite building blocks of 2′‐amino‐2′‐deoxyribonucleosides: New compounds for oligonucleotide synthesis

“…Staudinger reduction of the N, group in 10 and 11 led via migration of the npeoc group to 2'-deoxy-N4-{ [31] was used instead of PPh, in NH40H/ dioxan/pyridine [25].…”

“…In the uridine series, the N, function of the key building blocks 3 and 4 was reduced by Staudinger reduction to give 2'-amino-2'-deoxy-5'-0-(4-methoxytrity1)-(15) and 2'-amino-2'-deoxy-5'-0-(4,4-dimethoxytrityl)undine (16) [20] [25], respectively (Scheme 1). Selective protection of the 2'-amino function of 15 and 16 with the npeoc group was performed at 0" using 2-(4-nitrophenyl)ethyl chloroformate [26] , followed by the Staudinger reduction, also led to 17, due to migration of the npeoc group [27] to the amino function, to form a thermodynamically more stable carbamate structure than the original carbonate function.…”

“…The effects of 2'-amino substitution of nucleosides on oligomer-hybridization properties have not been sufficiently studied and are more interesting for further investigations, also against the background of catalytic ribozymes [8-101. We report here the synthesis of suitably protected 2'-amino-2'-deoxyribonucleotide phosphoramidite building blocks and their use in the solid-phase synthesis of 2'-aminomodified oligomers using the npe/npeoc strategy [I I] [12]. The aglycones and the 2'amino function were protected using the 2-(4-nitrophenyl)ethyl (npe) and the 2-(4-nitro-pheny1)ethoxycarbonyI (npeoc) groups which proved to be very efficient for the protection of amino groups in the 3'-[13-15] and 5'-position of nucleosides [16] as well (25), which was then protected at the 5'-OH position with (MeO),TrCl/DMAP in pyridine to give the desired nucleoside 26. The 2'-amino-2'-deoxyadenosine series was synthesized starting from 2'-azido-2'-deoxy-3',5'-0-(1 ,I ,3,3-tetraisopropyldisiloxane-l,3-diyl)adenosine (28) which was prepared by a multistep procedure as described in [32], except that the (trifluoromethy1)sulfonylation step was slightly modified.…”