methyl-5-O-tert-butyldiphenylsilyl-2-deoxy-ribo-furanoside | 127306-47-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl-5-O-tert-butyldiphenylsilyl-2-deoxy-ribo-furanoside
• 英文别名: methyl 5-O-(tert-butyldiphenylsilyl)-2-deoxy-D-riboside；(2R,3S)-2-(((tert-butyldiphenylsilyl)oxy)methyl)-5-methoxytetrahydrofuran-3-ol；methyl-2-deoxy-5-O-tert-butyldiphenylsilyl-D-ribofuranoside；methyl 5-O-t-butyldiphenylsilyl-2-deoxy-d-erythro-pentofuranoside；(2R,3S)-2-[[tert-butyl(diphenyl)silyl]oxymethyl]-5-methoxyoxolan-3-ol
• CAS: 127306-47-2
• 化学式: C₂₂H₃₀O₄Si
• 分子量: 386.563
• InChiKey: AEDSCEUXZVLWFU-MCOCGALXSA-N

物化性质

• 沸点：
  464.7±45.0 °C(Predicted)
• 密度：
  1.11±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.69
• 重原子数：
  27
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  47.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl-5-O-tert-butyldiphenylsilyl-2-deoxy-ribo-furanoside 在 sodium hydroxide 、 乙二胺四乙酸 、 DL-dithiothreitol 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 甲醇 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 57.0h， 生成 methyl 2,3-dideoxy-3-methylthio-5-O-(tert-butyldiphenylsilyl)-D-erythro-pentafuranoside
  参考文献：
  名称：

  Convergent synthesis of 2′,3′-dideoxy-3′-methylthio and 2′,3′-dideoxy-3′-mercapto nucleosides and their disulfide analogues — Potential anti-HIV agents

  摘要：

  The iodide 4(alpha) or 7 synthesized in three steps from 2-deoxy-D-ribose 1, has been subjected to a number of nucleophilic substitution reactions producing the 3-benzoylthio-, 3-methylthio- and the 3-thiocyanato-2,3-dideoxy-D-erythro-pentofuranosides 8,13 and 15, respectively, in addition to the disulfide 17 of their 3-mercapto analogue. Subjecting the thiobenzoate 8 to the Friedel-Crafts catalyzed silyl Hilbert Johnson reaction in conjunction with the silylated nucleobases of uracil, thymine and N4-isobutyrylcytosine 9a-c resulted in the isolation of the 2',3'-dideoxy-3'-mercapto nucleosides 11 and their disulfides 12 subsequent to deprotection. The 2,3-dideoxy-3-methylthio-pentofuranoside 13 afforded both anomers of the 2',3'-dideoxy-3'-methylthio nucleosides 19 and 20 under similar conditions. The first known example of a coupling directly on a 2,3-didehydro-2,3-dideoxyfuranose is presented. 2',3'-Dideoxy-3'-mercaptocytidine showed protection against HIV-1 in MT-4 cells with ED50 = 20 muM.

  DOI：

  10.1007/bf00808508
• 作为产物：
  描述：

  2-deoxy-D-ribose 在 吡啶 、 盐酸 、 4-二甲氨基吡啶 作用下， 反应 2.33h， 生成 methyl-5-O-tert-butyldiphenylsilyl-2-deoxy-ribo-furanoside
  参考文献：
  名称：

  1-[（2-羟基乙氧基）甲基] -6-（苯硫基）胸腺嘧啶的新型6-苄基尿嘧啶类似物的合成及有效的抗HIV-1活性。

  摘要：

  由相应的芳基乙腈和2-溴酸酯合成2-烷基-4-芳基-3-氧代丁酸乙酯。丁酸酯与硫脲的缩合，然后用氯乙酸处理，得到5-烷基-6-（芳基甲基）尿嘧啶。使用三氟甲磺酸三甲基甲硅烷基酯（TMS三氟甲磺酸酯）作为催化剂，将尿嘧啶与乙缩醛缩合，得到无环的5-烷基-6-（芳基甲基）尿嘧啶衍生物。还将6-苄基-5-乙基尿嘧啶与5-O-（叔丁基二苯基甲硅烷基）-2-脱氧-3-O-（苯氧硫羰基+++）-α，β-D-赤型戊呋喃糖苷缩合，然后进行巴顿还原脱保护，得到6-苄基-5-乙基-2′，3′-二脱氧尿苷的异构体。用烷基氯甲基硫化物将尿嘧啶烷基化，得到了HEPT的新硫代类似物。测试了所有新的N1取代的尿嘧啶对HIV-1的活性，

  DOI：

  10.1021/jm9600499

文献信息

• Efficient procedure for the synthesis of erythro and threo furanoid glycals from 2-deoxyribose
  作者：Mohamed Kassou、Sergio Castillón

  DOI：10.1016/s0040-4039(00)73538-6

  日期：1994.7

  Differently protected erythro and threo furanoid glycals have been synthesised starting from 2-deoxyribose, via selenoxide elimination as the key step.

  从2-脱氧核糖开始，通过亚硒酸盐的消除，合成了受不同保护的赤藓和苏糖类呋喃糖，这是关键步骤。
• New Synthesis of 2',3'-Didehydro-2',3'-dideoxynucleosides.
  作者：Ahmed E. S. Abdel-Megied、Poul Hansen、Erik B. Pedersen、Carsten M. Nielsen、Hugh Brian Dunford、Nils Åge Frøystein、George W. Francis、Britt Karlsson

  DOI：10.3891/acta.chem.scand.45-1060

  日期：——

  The 3'-iodonucleoside 4 and the 3'-O-methylsulfonylthymidine 9 have been synthesized by condensation of silylated uracils 2 with methyl 5-O-tert-butyldiphensilyl-2,3-dideoxy-3-iodo-D-threo-pentofuran oside (3) and methyl 5-O-tert-butyldiphenylsilyl-2-deoxy-3-methylsulfonyl-D-erythro- pentofuranoside (8), respectively. The nucleoside 4 and 9 produced the corresponding 2',3'-didehydro-2',3'-dideoxynucleosides

  3'-碘核苷4和3'-O-甲基磺酰基胸苷9是通过将甲硅烷基化的尿嘧啶2与5-O-叔丁基二苯甲硅烷基-2,3-二脱氧-3-碘-D-苏-戊呋喃糖苷缩合而合成的（3）和甲基5-O-叔丁基二苯基甲硅烷基-2-脱氧-3-甲基磺酰基-D-季戊基呋喃呋喃糖苷（8）。在用甲醇钠处理的消除反应中，核苷4和9产生了相应的2'，3'-二氢-2'，3'-二脱氧核苷5。化合物5b对HIV-1没有抗病毒活性。
• Pyrimidine intermediates
  申请人：Medivir AB

  公开号：US05440040A1

  公开（公告）日：1995-08-08

  The present invention is directed to compounds of formula (I), ##STR1## wherein R.sup.1 is OH, NH.sub.2 ; R.sup.2 is a heteroaromatic or aromatic substituent; R.sup.3 is H, OH, F, OCH.sub.3 ; R.sup.4 is H, F, OH or an ether or ester residue thereof, OCH.sub.3, CN, C.dbd.CH, N.sub.3 ; R.sup.5 is OH or an ether or ester residue thereof including mono, di- and triphosphate esters (.alpha.), wherein n is 0 or 1 and M is hydrogen or a pharmaceutically acceptable counterion such as sodium, potassium, ammonium or alkylammonium; and pharmaceutically acceptable salts thereof; and pharmaceutical compositions comprising said compounds can be used for therapeutic treatment of virus infections. The present invention is also directed to compounds of formula (I'), ##STR2## wherein R.sup.1 and R.sup.2 are as defined above, as intermediates.

  本发明涉及公式(I)的化合物：##STR1## 其中R.sup.1是OH，NH.sub.2；R.sup.2是杂芳基或芳基取代基；R.sup.3是H，OH，F，OCH.sub.3；R.sup.4是H，F，OH或其醚或酯残基，OCH.sub.3，CN，C.dbd.CH，N.sub.3；R.sup.5是OH或其醚或酯残基，包括单、二和三磷酸酯（.alpha.），其中n是0或1，M是氢或药用可接受的反离子，如钠、钾、铵或烷基铵；以及药用可接受的盐；包含这些化合物的药物组合物可用于治疗病毒感染。本发明还涉及公式(I')的化合物：##STR2## 其中R.sup.1和R.sup.2如上定义，作为中间体。
• An organocatalytic approach to the core of eunicellin
  作者：Ryan Gilmour、Timothy J. Prior、Jonathan W. Burton、Andrew B. Holmes

  DOI：10.1039/b709322e

  日期：——

  A stereocontrolled synthesis of the core of eunicellin is described featuring a Claisen rearrangement and a diastereoselective organocatalytic Diels–Alder reaction as the key steps.

  描述了一种通过Claisen重排和手性选择性有机催化Diels-Alder反应作为关键步骤的双立体控制合成尤尼细胞素核心的方法。
• β-Anomer selectivity in 2′-deoxynucleoside synthesis: A novel approach using an acyl carbamate directing group
  作者：Robert J. Young、Sue Shaw-Ponter、George W. Hardy、Gail Mills

  DOI：10.1016/s0040-4039(00)78472-3

  日期：1994.11

  Glycosylation of silylated pyrimidines using a phenyl 2-deoxy-3-O-(N-benzoyl)carbamoyl-1-thio-D-erythro-pentofuranoside yielded 2-deoxy-β-ribonucleosides in good yields with excellent anomeric selectivity. This prototype 3-O-carbamate directing group was readily formed and removed in high yields.

  使用苯基2-脱氧-3- O-（N-苯甲酰基）氨基甲酰基-1-硫代-D-赤型戊呋喃糖苷对甲硅烷基化的嘧啶进行糖基化反应，可以以良好的收率和优异的异头异构选择性产生2-脱氧-β-核糖核苷。该原型3- O-氨基甲酸酯引导基很容易形成并以高收率除去。