Synthesis of 2'-O-(1,3-benzodithiol-2-yl)uridine and related compounds as key intermediates in oligoribonucleotide synthesis

Regioselective O2′,O3′‐Deacetylations of Peracetylated Ribonucleosides by Using Tetra‐n‐butylammonium Fluoride

“…The robust, mild, efficient, and regioselective TBAF‐promoted deacetylation of 1,2‐diol diacetate provided convenient one‐step access to O 5′‐acetyl ribonucleosides in good yields. Through this procedure, a wide diversity of O 5′‐acetyl ribonucleosides are now available for the synthesis of oligoribonucleotides,4 deoxynucleosides,5 and cyclic nucleosides 6. Furthermore, this method offers the dependability and robustness of a non‐enzymatic chemical method for the selective deacetylation of peracetylated 2′‐deoxyribonucleosides.…”

“…Therefore, for the successful automated synthesis of oligonucleotides or the conventional multistep synthesis of ribonucleosides, appropriate protection of these functional groups is mandatory. The synthesis of O 5′‐acetyl ribonucleosides has gained considerable attention, as they are key intermediates in the synthesis of biomedically important molecules such as oligoribonucleotides,4 deoxynucleosides,5 and cyclic nucleosides 6. Although there are efficient methods for the selective deacetylation of the O 5′‐position while preserving the O 2′, O 3′ acyl groups, there are only a few protocols that can achieve the selective deacetylation of the O 2′, O 3′‐positions without affecting the O 5′‐acetate 7.…”

Selective Removal of the 2‘- and 3‘-O-Acyl Groups from 2‘,3‘,5‘-Tri-O-acylribonucleoside Derivatives with Lithium Trifluoroethoxide1

“…It is noteworthy that the low nucleophilicity of CF 3 CH 2 O - makes this methodology tolerant of a 4-amino group and the 5,6-double bond in pyrimidines, the 6-(imidazol-1-yl) group on purines, and the fused furan moiety in a furo[2,3- d ]pyrimidin-2(3 H )-one derivative. A broad variety of 5‘- O -acyl nucleoside derivatives are now readily available as intermediates for synthesis of deoxynucleosides, cyclic nucleosides, oligoribonucleotides, and nucleoside prodrugs. They also can be functionalized into numerous other compounds via 2‘,3‘- O -(dibutylstannylene) derivatives .…”

Synthesis of short oligoribonucleotides bearing a 3'- or 5'-terminal phosphate by use of 4,4',4"-tris(4,5-dichlorophthalimido)trityl as a new 5'-hydroxyl protecting group

“…Supplementary Material Available: Table III showing NMR spectral data and elemental analyses of compounds [3][4][5][6][7][8][9] and Figure 1 showing the HLPC profile of AUAp (5 pages). Ordering information is given on any current masthead page.…”