5-O-benzoyl-1,2-di-O-acetyl-3-O-methanesulfonyl-α/β-D-xylofuranose | 177949-07-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 5-O-benzoyl-1,2-di-O-acetyl-3-O-methanesulfonyl-α/β-D-xylofuranose
• 英文别名: [(2R,3S,4R)-4,5-diacetyloxy-3-methylsulfonyloxyoxolan-2-yl]methyl benzoate
• CAS: 177949-07-4
• 化学式: C₁₇H₂₀O₁₀S
• 分子量: 416.406
• InChiKey: MPMSJALMPDGKIX-AWVCJSPBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  28
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  140
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  5-O-benzoyl-1,2-di-O-acetyl-3-O-methanesulfonyl-α/β-D-xylofuranose 在 吡啶 、 硫酸 、 四氯化锡 作用下， 以 水 、 乙腈 为溶剂， 反应 56.0h， 生成 1-(5'-O-benzoyl-2',3'-di-O-methylsulfonyl-β-D-xylofuranosyl)thymine
  参考文献：
  名称：

  Mustafin; Gataullin; Spirikhin, Russian Journal of Organic Chemistry, 1996, vol. 32, # 12, p. 1784 - 1790

  摘要：

  DOI：
• 作为产物：
  描述：

  异恶唑，3-isocyanato-5-(1-methylethyl)-(9CI) 在 吡啶 、 硫酸 、 三乙胺 、 丙酮 、 三氟乙酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 5-O-benzoyl-1,2-di-O-acetyl-3-O-methanesulfonyl-α/β-D-xylofuranose
  参考文献：
  名称：

  Synthesis and comparative evaluation of two antiviral agents: β-l-Fd4C and β-d-Fd4C

  摘要：

  The synthesis of beta-D-Fd(4)C was achieved in a stereoselective fashion fi om D-xylose. The antiviral activity and cytotoxicity of beta-D-Fd(4)C was compared with that of beta-L-Fd(4)C and 3TC (Lamivudine). Of the three agents compared, beta-L-Fd(4)C was found to be the most potent antiviral agent. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0960-894x(98)00599-x

文献信息

• 2,3-Anhydro Sugars in Glycoside Bond Synthesis. Highly Stereoselective Syntheses of Oligosaccharides Containing α- and β-Arabinofuranosyl Linkages
  作者：Rajendrakumar Reddy Gadikota、Christopher S. Callam、Timothy Wagner、Brian Del Fraino、Todd L. Lowary

  DOI：10.1021/ja029302m

  日期：2003.4.1

  biologically important events mediated by carbohydrates has generated great interest in the synthesis of oligosaccharides and the development of new methods for glycosidic bond formation. In this paper, we report that 2,3-anhydrofuranose thioglycosides (1, 5) and glycosyl sulfoxides (2, 6), in which the hydroxyl groups C-2 and C-3 are “protected” as an epoxide, glycosylate alcohols with an exceptionally

  由碳水化合物介导的生物学重要事件的不断发现引起了人们对寡糖合成和糖苷键形成新方法开发的极大兴趣。在本文中，我们报告了 2,3-脱水呋喃糖硫糖苷 (1, 5) 和糖基亚砜 (2, 6)，其中羟基 C-2 和 C-3 被“保护”为环氧化物，糖基化醇与极高的立体声控制度。与这种全新类型的糖基化剂反应的主要或唯一产物是其中新形成的糖苷键与环氧化物部分顺式。我们进一步证明，随后环氧化物部分的亲核打开在碱性条件下进行，以高产率和良好至极好的区域选择性得到产物。主要的开环产物具有阿拉伯立体化学，因此该方法构成了合成阿拉伯呋喃糖苷的新方法。在环...
• Chemical synthesis of 13C-labelled monomers for the solid-phase and template controlled enzymatic synthesis of DNA and RNA oligomers
  作者：S. Quant、R.W. Wechselberger、M.A. Wolter、K.-H. Wörner、P. Schell、J.W. Engels、C. Griesinger、H. Schwalbe

  DOI：10.1016/s0040-4039(00)73458-7

  日期：1994.9

  5′-O-dimethoxytrityl protected DNA-phosphoramidites and 5′-O-dimethoxytrityl-2′-O-trialkylsilyl protected RNA-phosphor-amidites for the solid phase synthesis of DNA- and RNA-oligomers and to 5′-O-ribo- and deoxyribo-nucleosidetriphosphates for template controlled enzymatic synthesis (polymerase- or reverse transcriptase reaction) has been carried out.

  从[ 13 C 6 ]-葡萄糖1和相应的核碱基5a-e或6a-e（N 6-苯甲酰基-腺嘌呤，N 2-乙酰基-鸟嘌呤，N 4-苯甲酰基-胞嘧啶）开始制备13 C标记的核糖核苷（尿嘧啶和胸腺嘧啶）的总收率在47％至66％之间。它们随后转化为5'- O-二甲氧基三苯甲基保护的DNA-亚磷酰胺和5'- O-二甲氧基三苯甲基-2' - O-三烷基甲硅烷基保护的RNA-磷-酰胺，用于固相合成DNA-和RNA-低聚物，并转化为5' - Ø已经进行了用于模板控制的酶促合成（聚合酶-或逆转录酶反应）的-核糖核苷和-核糖核苷三磷酸。
• Synthesis of 5-Phenyl-2(1H)-pyrimidinone Nucleosides
  作者：Marcela Krečmerová、Hubert Hřebabecký、Milena Masojídková、Antonín Holý

  DOI：10.1135/cccc19960458

  日期：——

  Reaction of 2-phenyltrimethinium salt 1 with thiourea and subsequent reaction with chloroacetic acid afforded 5-phenyl-2(1H)-pyrimidinone (3). Its silyl derivative 4 was condensed with 1-O-acetyl-2,3,5-tri-O-benzoyl-D-ribofuranose under catalysis with tin tetrachloride or trimethylsilyl trifluoromethanesulfonate to give protected nucleoside 5 together with 5',O⁶-cyclo-5-phenyl-1,3-bis- (β-D-ribofuranosyl)-6-hydroxy-5,6-dihydro-2(1H,3H)-pyrimidinone (7). The greatest amounts of 7 were formed with the latter catalyst. Nucleosidation of the silyl derivative 4 with protected methyl 2-deoxy-D-ribofuranoside 8 or 2-deoxy-D-ribofuranosyl chloride 9 afforded 1-(2-deoxy-3,5-di-O-p-toluoyl-β-D-ribofuranosyl)-5-phenyl-2(1H)-pyrimidinone (10) and its α-anomer 11. Reaction of 10 and 11 with methanolic ammonia gave free 2'-deoxynucleosides 12 and 13. Compound 13 was converted into 5'-O-tert-butyldiphenylsilyl-3'-O-mesyl derivative 14 which on heating with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and subsequent cleavage with tetrabutylammonium fluoride afforded 2',3'-dideoxy-2',3'-didehydronucleoside 15. Reaction of the silyl derivative 4 with 1,2-di-O-acetyl-3,5-di-O-benzoylxylofuranose (18), catalyzed with tin tetrachloride, furnished 1-(2-O-acetyl-3,5-di-O-benzoyl-β-D-xylofuranosyl)-2(1H)-pyrimidinone (19) which was deprotected to give the β-D-xylofuranosyl derivative 22. As a side product, the nucleosidation afforded the β-D-xylopyranosyl derivative 23. Deacetylation of compound 19 gave 1-(3,5-di-O-benzoyl-β-D-xylofuranosyl)-5-phenyl-2(1H)-pyrimidinone (24) which on reaction with thionyl chloride afforded 2'-chloro-2'-deoxynucleoside 25 and 2',O⁶-cyclonucleoside 26. Heating of compound 25 with DBU in dimethylformamide furnished the lyxo-epoxide 27 which on reaction with methanolic ammonia was converted into free 1-(2,3-anhydro-β-D-lyxofuranosyl)-5-phenyl-2(1H)-pyrimidinone (28). Reaction of 1,2-di-O-acetyl-5-O-benzoyl-3-O-methanesulfonyl-D-xylofuranose (30) with silyl derivative 4 gave the nucleoside 31 which by treatment with DBU was converted into an equilibrium mixture of 5'-benzoylated arabinofuranoside 33a and its 2',6-anhydro derivative 33b.

  2-苯基三甲基铵盐1与硫脲反应，随后与氯乙酸反应，得到5-苯基-2（1H）-嘧啶酮（3）。其硅烷衍生物4在锡四氯化物或三甲基三氟甲磺酸硅烷酯的催化下与1- O-乙酰基-2,3,5-三- O-苯甲酰-D-核糖呋喃酮缩合，得到受保护的核苷5，以及5'，O6-环-5-苯基-1,3-双（β-D-核糖呋喃基）-6-羟基-5,6-二氢-2（1H，3H）-嘧啶酮（7）。后一催化剂形成的7最多。硅烷衍生物4与受保护的甲基2-脱氧-D-核糖呋喃苷8或2-脱氧-D-核糖呋喃基氯化物9核苷化，得到1-（2-脱氧-3,5-二-O- p-甲苯基-β-D-核糖呋喃基）-5-苯基-2（1H）-嘧啶酮（10）及其α异构体11。10和11与甲醇氨反应，得到游离的2'-脱氧核苷12和13。化合物13转化为5'- O- tert-丁基二苯基硅烷基-3'- O-甲磺酰基衍生物14，经DBU加热和四丁基铵氟化物裂解，得到2'，3'-二去氧-2'，3'-二脱氢核苷15。硅烷衍生物4与1,2-二-O-乙酰-3,5-二-O-苯甲酰木糖呋喃酮（18）在锡四氯化物的催化下反应，得到1-（2-O-乙酰-3,5-二-O-苯甲酰-β-D-木糖呋喃基）-2（1H）-嘧啶酮（19），去保护后得到β-D-木糖呋喃基衍生物22。作为副产物，核苷化产生了β-D-木糖吡喃基衍生物23。化合物19的脱乙酰化反应得到1-（3,5-二-O-苯甲酰-β-D-木糖呋喃基）-5-苯基-2（1H）-嘧啶酮（24），与氯化硫酰反应得到2'-氯-2'-脱氧核苷25和2'，O6-环核苷26。化合物25在二甲基甲酰胺中与DBU加热，得到lyxo-环氧化物27，与甲醇氨反应得到自由的1-（2,3-脱水-β-D-lyxofuranosyl）-5-苯基-2（1H）-嘧啶酮（28）。1,2-二-O-乙酰-5-O-苯甲酰-3-O-甲磺酰-D-木糖呋喃酮（30）与硅烷衍生物4反应，经DBU处理后转化为5'-苯甲酰化的阿拉伯糖呋喃核苷33a及其2',6-脱水衍生物33b的平衡混合物。