Synthesis of 1′#,2′,3′,4′#,5′,5″-2H6-β-D-ribonucleosides and 1′#, 2′,2″,3′,4′#,5′,5″-2H7-β-D-2′-deoxyribonucleosides for selective suppression of proton resonances in partially-deuterated oligo-DNA, oligo-RNA and in 2,5A core (1H-NMR window)
作者:András Földesi、Frans Peder R. Nilson、Corine Glemarec、Carlo Gioeli、Jyoti Chattopadhyaya
DOI:10.1016/s0040-4020(01)82001-9
日期:1992.1
1′#,2′,3′,4′#,5′,5″-2H6-ribonucleosides 13 – 16 were converted in high yields to the corresponding 1′#,2′,2″,3′,4′#,5′,5″-2H7-2′-deoxynucleosides 41 – 44 in the following manner: 3′,5′-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl (TPDS))-1′#,2′,3′,4#′,5′,5″-2H6-nucleosides 29 – 32 were converted to the corresponding 2′-O-phenoxythiocarbonyl derivatives 33 – 36, which were deoxygenated by tri-n-butyltin
阮内镍-2 H 2 O在甲基α/β-D-呋喃核糖苷[α/β= 〜3:10] 1的差向异构体混合物上的交换反应产生了甲基1 #,2,3,4 #,5,5'- 2 H 6 -α/β-呋喃核糖苷2 [在C2,C3,C5 / 5'处为97原子%2 H;C 4(C4 #)〜85原子%2 H ;在C1(C1 #)]处约20个原子%2 H,以60 – 80%的产率获得,同时还得到了差向异构的木糖和阿拉伯糖副产物。在干燥的吡啶中将粗产物2甲苯磺酸化,并在硅胶柱上小心分离,得到纯的1-O-甲基-2,3,5-三-O-(4-甲苯甲酰基)-α/β-D-1#,2,3,4 #,5,5'- 2 H 6-核呋喃糖苷4(48%)。4转化为1-O-乙酰基-2,3,5-三-O-甲苯甲酰基-α/β-D-1 #,2,3,4 #,5,5'- 2 H 6-核呋喃糖苷6( 82%的人提供了合成氘核糖核苷用于RNA或DNA合成的关键组成部分。然后将化合物6与甲硅烷基尿嘧啶,N