THE AUTOMATED SYNTHESIS OF SULFUR-CONTAINING OLIGODEOXYRIBONUCLEOTIDES USING 3H-1,2-BENZODITHIOL-3-ONE 1,1-DIOXIDE AS A SULFUR-TRANSFER REAGENT
THE AUTOMATED SYNTHESIS OF SULFUR-CONTAINING OLIGODEOXYRIBONUCLEOTIDES USING 3H-1,2-BENZODITHIOL-3-ONE 1,1-DIOXIDE AS A SULFUR-TRANSFER REAGENT
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DOI：
10.1021/jo00302a039
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发表时间：
1990-07-20
影响因子：
3.6
通讯作者：
BEAUCAGE, SL
中科院分区：
文献类型：
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作者：
IYER, RP;PHILLIPS, LR;BEAUCAGE, SL
在通过“脱氧核糖核苷亚磷酰胺”方法自动合成寡脱氧核糖核苷硫代磷酸酯的过程中，测试了几种多硫化物作为潜在的硫转移试剂。硫代磺酸盐3H-1,2-苯并二硫醇-3-酮1,1-二氧化物(12)作为硫化剂特别有效。 12的0.2M乙腈溶液在30秒内以接近定量的产率将二核苷单亚磷酸三酯13a-d转化为相应的硫代磷酸酯15a-d。该试剂可快速、高效（逐步产率 99%）且可靠地自动合成与 HIV-1 rev 基因 mRNA 互补的硫代磷酸酯寡聚物（28 聚体），仅携带或携带预定数量的 P(S) 连接。此外，暴露于硫化试剂长时间处理（24小时）的寡聚物没有显示出任何可检测到的核苷碱基修饰。
Several polysulfides were tested as potential sulfur-transfer reagents during the automated synthesis of oligodeoxyribonucleoside phosphorothioates via the "deoxyribonucleoside phosphoramidite" approach. The thiosulfonate 3H-1,2-benzodithiol-3-one 1,1-dioxide (12) was particularly efficient as a sulfurizing reagent. A 0.2 M solution of 12 in acetonitrile converted the dinucleoside monophosphite triesters 13a-d into the corresponding phosphorothioates 15a-d within 30 s in near quantitative yields. This reagent led to rapid, efficient (stepwise yields of 99%), and reliable automated synthesis of phosphorothioate oligomers (28-mers) complementary to the mRNA of the HIV-1 rev gene, carrying either exclusively or a predetermined number of P(S) linkages. Additionally, oligomers exposed to prolonged treatment (24 h) with the sulfurizing reagent did not show any detectable modification of the nucleosidic bases.