含3'-硫代胸苷的二磷酸胸苷类似物的合成与性质
Synthesis and properties of dithymidine phosphate analogues containing 3'-thiothymidine.
作者信息
Cosstick R, Vyle J S
机构信息
Robert Robinson Laboratories, Department of Chemistry, University of Liverpool, UK.
出版信息
Nucleic Acids Res. 1990 Feb 25;18(4):829-35. doi: 10.1093/nar/18.4.829.
Abstract
Dithymidine-3'-S-phosphorothioate (d(TspT)) has been prepared from a 5'-O-monomethoxytritylthymidine-3'-S-phosphorothioamidite (7) by activation with 5-(p-nitrophenyl)tetrazole in the presence of 3'-O-acetylthymidine. The resulting dinucleoside phosphorothioite is readily oxidised to the corresponding 3'-S-phosphorothioate using either tetrabutylammonium (TBA) periodate or TBA oxone and has been deprotected under standard conditions to yield d(TspT). This dithymidine phosphate analogue is comparatively resistant to hydrolysis by nuclease P1, but the P-S bond is readily cleaved by aqueous solutions of either iodine or silver nitrate. Dithymidine-3'-S-phosphorodithioate (d[Tsp(s)T]) was prepared in an analogous fashion using sulphur to oxidise the intermediate dinucleoside phosphorothioite. Absolute stereochemistry has been assigned to the diastereoisomers of d[Tsp(s)T] by comparing their physical and chemical properties to those of the dinucleoside phosphorothioates.
摘要
3'-硫代磷酸二胸苷（d(TspT)）由5'-O-单甲氧基三苯甲基胸苷-3'-硫代磷酰胺亚基（7）在3'-O-乙酰胸苷存在下用5-(对硝基苯基)四唑活化制备而成。所得的二核苷硫代磷酸酯用四丁基铵（TBA）高碘酸盐或TBA过氧单磺酸钾很容易氧化为相应的3'-硫代磷酸酯，并在标准条件下脱保护得到d(TspT)。这种磷酸二胸苷类似物相对耐核酸酶P1水解，但P-S键很容易被碘或硝酸银水溶液裂解。3'-二硫代磷酸二胸苷（d[Tsp(s)T]）以类似方式制备，使用硫氧化中间的二核苷硫代磷酸酯。通过将d[Tsp(s)T]的非对映异构体的物理和化学性质与二核苷硫代磷酸酯的性质进行比较，确定了其绝对立体化学结构。
相似文献
1
Synthesis and properties of dithymidine phosphate analogues containing 3'-thiothymidine.含3'-硫代胸苷的二磷酸胸苷类似物的合成与性质
Nucleic Acids Res. 1990 Feb 25;18(4):829-35. doi: 10.1093/nar/18.4.829.
2
The synthesis of di- and oligo-nucleotides containing a phosphorodithioate internucleotide linkage with one of the sulfur atoms in a 5'-bridging position.含有硫代磷酸二酯键且其中一个硫原子处于5'-桥连位置的二核苷酸和寡核苷酸的合成。
Org Biomol Chem. 2009 May 21;7(10):2162-9. doi: 10.1039/b901791g. Epub 2009 Mar 30.
3
Conformational studies of dithymidine boranomonophosphate diastereoisomers.
Bioorg Med Chem. 1997 May;5(5):787-95. doi: 10.1016/s0968-0896(96)00259-3.
4
Mung bean (Phaseolus aureus) nuclease. A mechanistic investigation of the DNA-cleavage reaction using a dinucleoside phosphorothioate.绿豆（Phaseolus aureus）核酸酶。使用二核苷硫代磷酸酯对DNA切割反应的机理研究。
Biochem J. 1987 Feb 1;241(3):827-33. doi: 10.1042/bj2410827.
5
An approach to the stereoselective synthesis of Sp-dinucleoside phosphorothioates using phosphotriester chemistry.一种利用磷酸三酯化学方法立体选择性合成 Sp-二核苷硫代磷酸酯的途径。
Nucleic Acids Res. 1987 Dec 10;15(23):9921-32. doi: 10.1093/nar/15.23.9921.
6
Stereoselective synthesis of dinucleoside boranophosphates by an oxazaphospholidine method.通过恶唑磷烷方法立体选择性合成二核苷硼酸磷酸酯。
Bioorg Med Chem Lett. 2006 Jun 15;16(12):3111-4. doi: 10.1016/j.bmcl.2006.03.076. Epub 2006 Apr 18.
7
Stereoselective synthesis of P-homochiral oligo(thymidine methanephosphonates).P-同手性寡聚（胸苷甲膦酸酯）的立体选择性合成。
Nucleic Acids Res. 1988 Dec 23;16(24):11675-89. doi: 10.1093/nar/16.24.11675.
8
Stereochemistry of internucleotide bond formation by the H-phosphonate method. 1. Synthesis and 31P NMR analysis of 16 diribonulceoside (3'-5')-H-phosphonates and the corresponding phosphorothioates.通过H-膦酸酯法形成核苷酸间键的立体化学。1. 16种二核糖核苷（3'-5'）-H-膦酸酯及相应硫代磷酸酯的合成与31P NMR分析。
Nucleosides Nucleotides Nucleic Acids. 2005;24(10-12):1469-84. doi: 10.1080/15257770500265729.
9
Synthesis of nucleic acid methylphosphonates via the 1-hydroxybenzotriazole phosphotriester approach.通过1-羟基苯并三唑磷酸三酯法合成核酸甲基膦酸酯。
Nucleic Acids Res. 1986 Mar 11;14(5):2171-85. doi: 10.1093/nar/14.5.2171.
10
Synthesis of d(GC) and d(CG) octamers containing alternating phosphorothioate linkages: effect of the phosphorothioate group on the B-Z transition.含交替硫代磷酸酯键的d(GC)和d(CG)八聚体的合成：硫代磷酸酯基团对B-Z转变的影响
Biochemistry. 1985 Jul 2;24(14):3630-8. doi: 10.1021/bi00335a035.
引用本文的文献
1
Solid-phase synthesis and structural characterisation of phosphoroselenolate-modified DNA: a backbone analogue which does not impose conformational bias and facilitates SAD X-ray crystallography.磷硒酸酯修饰DNA的固相合成与结构表征：一种不会产生构象偏向且有助于单波长反常散射X射线晶体学研究的主链类似物。
Chem Sci. 2019 Oct 11;10(47):10948-10957. doi: 10.1039/c9sc04098f. eCollection 2019 Dec 21.
2
Arginine as a general acid catalyst in serine recombinase-mediated DNA cleavage.精氨酸作为丝氨酸重组酶介导的 DNA 切割中的通用酸催化剂。
J Biol Chem. 2013 Oct 4;288(40):29206-14. doi: 10.1074/jbc.M113.508028. Epub 2013 Aug 22.
3
Sin resolvase catalytic activity and oligomerization state are tightly coupled.未解决的催化活性和寡聚状态紧密相关。
J Mol Biol. 2010 Nov 19;404(1):16-33. doi: 10.1016/j.jmb.2010.08.057. Epub 2010 Sep 22.
4
Identification of catalytic metal ion ligands in ribozymes.核酶中催化金属离子配体的鉴定。
Methods. 2009 Oct;49(2):148-66. doi: 10.1016/j.ymeth.2009.07.005. Epub 2009 Aug 3.
5
Synthesis of phosphorothioamidites derived from 3'-thio-3'-deoxythymidine and 3'-thio-2',3'-dideoxycytidine and the automated synthesis of oligodeoxynucleotides containing a 3'-S-phosphorothiolate linkage.源自3'-硫代-3'-脱氧胸苷和3'-硫代-2',3'-二脱氧胞苷的硫代磷酰胺的合成以及含3'-S-硫代磷酸酯键的寡脱氧核苷酸的自动化合成。
Nucleic Acids Res. 2004 Jan 23;32(2):495-501. doi: 10.1093/nar/gkh189. Print 2004.
6
Active site constraints in the hydrolysis reaction catalyzed by bacterial RNase P: analysis of precursor tRNAs with a single 3'-S-phosphorothiolate internucleotide linkage.细菌核糖核酸酶P催化的水解反应中的活性位点限制：对具有单个3'-硫代磷酸酯核苷酸间连接的前体tRNA的分析
Nucleic Acids Res. 2000 Feb 1;28(3):720-7. doi: 10.1093/nar/28.3.720.
7
Metal ion catalysis during group II intron self-splicing: parallels with the spliceosome.II类内含子自我剪接过程中的金属离子催化：与剪接体的相似之处
Genes Dev. 1999 Jul 1;13(13):1729-41. doi: 10.1101/gad.13.13.1729.
8
Chemical and enzymatic properties of bridging 5'-S-phosphorothioester linkages in DNA.DNA中桥连5'-S-硫代磷酸酯键的化学和酶学性质
Nucleic Acids Res. 1998 Jul 1;26(13):3159-64. doi: 10.1093/nar/26.13.3159.
9
Cleavage properties of an oligonucleotide containing a bridged internucleotide 5'-phosphorothioate RNA linkage.
Nucleic Acids Res. 1995 Dec 11;23(23):4753-60. doi: 10.1093/nar/23.23.4753.
10
Synthesis and selective cleavage of an oligodeoxynucleotide containing a bridged internucleotide 5'-phosphorothioate linkage.
Nucleic Acids Res. 1991 Apr 11;19(7):1437-41. doi: 10.1093/nar/19.7.1437.
本文引用的文献
1
Polymer support oligonucleotide synthesis XVIII: use of beta-cyanoethyl-N,N-dialkylamino-/N-morpholino phosphoramidite of deoxynucleosides for the synthesis of DNA fragments simplifying deprotection and isolation of the final product.聚合物载体寡核苷酸合成 XVIII：脱氧核苷的β-氰基乙基-N，N-二烷基氨基-/N-吗啉代亚磷酰胺用于 DNA 片段合成，简化最终产物的脱保护和分离
Nucleic Acids Res. 1984 Jun 11;12(11):4539-57. doi: 10.1093/nar/12.11.4539.
2
[The inhibitory cholinergic innervation of the dilator on the movement of the pupil].[瞳孔开大肌上抑制性胆碱能神经支配对瞳孔运动的影响]
Nippon Ganka Gakkai Zasshi. 1984 Dec;88(12):1555-7.
3
Some substrate properties of analogues of oligothymidylates with p-s-C5' bonds.具有对硫代-C5'键的寡聚胸苷酸类似物的一些底物特性。
Nucleic Acids Res. 1981 Jan 10;9(1):189-201. doi: 10.1093/nar/9.1.189.
4
Nucleoside S-alkyl phosphorothioates. II. Preparation and chemical and enzymatic properties.
J Am Chem Soc. 1969 Mar 12;91(6):1522-7. doi: 10.1021/ja01034a040.
5
Nucleophilic reactions of some nucleoside phosphorothioates.
J Am Chem Soc. 1972 Mar 22;94(6):2079-85. doi: 10.1021/ja00761a047.
6
Chemical synthesis of oligonucleotides containing a free sulphydryl group and subsequent attachment of thiol specific probes.含有游离巯基的寡核苷酸的化学合成及硫醇特异性探针的后续连接。
Nucleic Acids Res. 1985 Jun 25;13(12):4485-502. doi: 10.1093/nar/13.12.4485.
7
Phosphorothioate analogs of oligodeoxynucleotides: inhibitors of replication and cytopathic effects of human immunodeficiency virus.寡脱氧核苷酸的硫代磷酸酯类似物：人类免疫缺陷病毒复制及细胞病变效应的抑制剂
Proc Natl Acad Sci U S A. 1987 Nov;84(21):7706-10. doi: 10.1073/pnas.84.21.7706.
8
Phosphorothioates in molecular biology.
Trends Biochem Sci. 1989 Mar;14(3):97-100. doi: 10.1016/0968-0004(89)90130-8.
9
Nucleoside phosphorothioates.硫代磷酸核苷
Annu Rev Biochem. 1985;54:367-402. doi: 10.1146/annurev.bi.54.070185.002055.
10
The use of s-2-cyanoethyl phosphorothioate in the preparation of oligo 5'-deoxy-5'-thiothymidylates.S-2-氰基乙基硫代磷酸酯在制备寡聚5'-脱氧-5'-硫代胸苷酸中的应用。
Nucleic Acids Res. 1975 Jan;2(1):1-9. doi: 10.1093/nar/2.1.1.
Zotero 插件