1,4-anhydro-1-(tert-butyldimethylsilyloxymethyl)-2-deoxy-3,5-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-4-thio-D-erythropento-1-enitol | 474409-49-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氢噻吩类
• 英文名称: 1,4-anhydro-1-(tert-butyldimethylsilyloxymethyl)-2-deoxy-3,5-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-4-thio-D-erythropento-1-enitol
• 英文别名: [(6aR,9aS)-2,2,4,4-tetra(propan-2-yl)-6a,9a-dihydro-6H-thieno[3,2-f][1,3,5,2,4]trioxadisilocin-8-yl]methoxy-tert-butyl-dimethylsilane
• CAS: 474409-49-9
• 化学式: C₂₄H₅₀O₄SSi₃
• 分子量: 518.981
• InChiKey: IEDQIOUTGTVZNJ-XZOQPEGZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.96
• 重原子数：
  32
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  62.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1,4-anhydro-1-(tert-butyldimethylsilyloxymethyl)-2-deoxy-3,5-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-4-thio-D-erythropento-1-enitol 在 三乙基硼 、 四丁基氟化铵 、 氨 、 三正丁基氢锡 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 乙腈 、 苯 为溶剂， 生成 4'-thioangustmycin
  参考文献：
  名称：

  立体选择性地从4-硫呋喃类化合物糖基进入1'- C-支链的4'-硫代核苷：合成4'-硫代angustmycin C

  摘要：

  已经开发了用于合成新型1' - C-碳取代的4'-硫代核苷的立体选择性合成方法。本方法包括以下步骤：（1）基于锂化制备1 - C-碳取代的4-硫呋喃类糖，和（2）NIS-或PhSeCl引发的对这些1-取代的糖的立体选择性糖苷化。该合成序列使我们能够合成抗肿瘤抗生素阿古霉素C的4'-硫代类似物。

  DOI：

  10.1016/s0040-4039(02)01131-0
• 作为产物：
  描述：

  1,4-anhydro-2-deoxy-3,5-O-(1,1,3,3-tetraisopropyldisiloxan-1,3-diyl)-4-thio-D-erythro-pent-1-enitol 在 咪唑 、 sodium tetrahydroborate 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 1.5h， 生成 1,4-anhydro-1-(tert-butyldimethylsilyloxymethyl)-2-deoxy-3,5-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-4-thio-D-erythropento-1-enitol
  参考文献：
  名称：

  Synthesis and antiviral activities of 1′-carbon-substituted 4′-thiothymidines

  摘要：

  4-Thiofuranoid glycals substituted at the 1-position with methyl (5), (t-butyldimethylsilyloxy)methyl (7), and acetoxymethyl (8) groups were prepared from the 3,5-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl) (TIPDS)-4-thiofuranoid glycal (3) by way of LDA-lithiation. N-Iodosuccimide-initiated electrophilic glycosidation between silylated thymine and these 1-carbon-substituted 4-thioglycals gave the respective beta-anomers (9, 10, and 13) stereo selectively. Tin radical-mediated removal of the T-iodine atom from these products provided the corresponding 1'-branched 4'-thiothymidine derivatives (11, 12, and 14) in good yields. The 1'-hydroxymethyl derivative (15) served as a precursor for the preparation of the formyl (16), cyanoethenyl (17), and cyano (19) derivatives. Among the deprotected 1'-branched 4'-thiothymidines (20-25), the 1'-methyl analogue 20 showed the most potent anti-HSV-1 activity, but it was much less active than the parent compound 4'-thiothymidine. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmc.2004.07.057

文献信息

• 4-Thiofuranoid Glycals: Versatile Synthons for Stereoselective Synthesis of 4′-Thionucleosides
  作者：Kazuhiro Haraguchi、Haruhiko Takahashi、Hiromichi Tanaka

  DOI：10.1081/ncn-120022629

  日期：2003.10

  beta-anomers of 4'-thionucleosides have been synthesized stereoselectively, through PhSeCl- or N-iodosuccimide (NIS)-initiated electrophilic glycosidation to 3,5-O-(di-t-butylsilylene)-4-thiofuranoid glycal (1). This synthetic method has been applied to the synthesis of those analogues branched at the anomeric position using 1-C-carbon-substituted 3,5-O-(tetraisopropyldisiloxane-1,3-diyl)-4-thiofuranoid glycals (11-14) prepared based on lithiation of 10.
• Synthesis and antiviral activities of 1′-carbon-substituted 4′-thiothymidines
  作者：Kazuhiro Haraguchi、Haruhiko Takahashi、Hiromichi Tanaka、Hiroyuki Hayakawa、Noriyuki Ashida、Takao Nitanda、Masanori Baba

  DOI：10.1016/j.bmc.2004.07.057

  日期：2004.10

  4-Thiofuranoid glycals substituted at the 1-position with methyl (5), (t-butyldimethylsilyloxy)methyl (7), and acetoxymethyl (8) groups were prepared from the 3,5-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl) (TIPDS)-4-thiofuranoid glycal (3) by way of LDA-lithiation. N-Iodosuccimide-initiated electrophilic glycosidation between silylated thymine and these 1-carbon-substituted 4-thioglycals gave the respective beta-anomers (9, 10, and 13) stereo selectively. Tin radical-mediated removal of the T-iodine atom from these products provided the corresponding 1'-branched 4'-thiothymidine derivatives (11, 12, and 14) in good yields. The 1'-hydroxymethyl derivative (15) served as a precursor for the preparation of the formyl (16), cyanoethenyl (17), and cyano (19) derivatives. Among the deprotected 1'-branched 4'-thiothymidines (20-25), the 1'-methyl analogue 20 showed the most potent anti-HSV-1 activity, but it was much less active than the parent compound 4'-thiothymidine. (C) 2004 Elsevier Ltd. All rights reserved.
• Stereoselective entry to 1′-C-branched 4′-thionucleosides from 4-thiofuranoid glycal: synthesis of 4′-thioangustmycin C
  作者：Kazuhiro Haraguchi、Haruhiko Takahashi、Hiromichi Tanaka

  DOI：10.1016/s0040-4039(02)01131-0

  日期：2002.8

  1′-C-carbon-substituted 4′-thionucleosides has been developed. The present method consists of the following steps: (1) preparation of the 1-C-carbon-substituted 4-thiofuranoid glycals based on lithiation, and (2) NIS- or PhSeCl-initiated stereoselective glycosidation to these 1-substituted glycals. This synthetic sequence enabled us to synthesize the 4′-thio analogue of antitumor antibiotic angustmycin

  已经开发了用于合成新型1' - C-碳取代的4'-硫代核苷的立体选择性合成方法。本方法包括以下步骤：（1）基于锂化制备1 - C-碳取代的4-硫呋喃类糖，和（2）NIS-或PhSeCl引发的对这些1-取代的糖的立体选择性糖苷化。该合成序列使我们能够合成抗肿瘤抗生素阿古霉素C的4'-硫代类似物。