5-O-(4-chlorobenzoyl)-1,2-O-isopropylidene-3-C-[2-(trimethylsilyl)ethynyl]-D-ribo-pentofuranose | 199787-16-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 5-O-(4-chlorobenzoyl)-1,2-O-isopropylidene-3-C-[2-(trimethylsilyl)ethynyl]-D-ribo-pentofuranose
• 英文别名: 5-O-(4-chlorobenzoyl)-3-C-(2-trimethylsilylethynyl)-1,2-isopropylidene-α-D-ribofuranose；[(3aR,5R,6R,6aR)-6-hydroxy-2,2-dimethyl-6-(2-trimethylsilylethynyl)-5,6a-dihydro-3aH-furo[2,3-d][1,3]dioxol-5-yl]methyl 4-chlorobenzoate
• CAS: 199787-16-1
• 化学式: C₂₀H₂₅ClO₆Si
• 分子量: 424.953
• InChiKey: PQIWDUXZOCUKLI-YNVMFWSZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.99
• 重原子数：
  28
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  74.2
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  5-O-(4-chlorobenzoyl)-1,2-O-isopropylidene-3-C-[2-(trimethylsilyl)ethynyl]-D-ribo-pentofuranose 在 4-二甲氨基吡啶 、 甲酸 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 7.75h， 生成 5-O-(4-chlorobenzoyl)-1,2,3-tri-O-isobutyryl-3-C-[2-(trimethylsilyl)ethynyl]-α-D-ribo-pentofuranose
  参考文献：
  名称：

  Nucleosides and nucleotides. Part 212: Practical large-scale synthesis of 1-(3-C-ethynyl-β-d-ribo-pentofuranosyl)cytosine (ECyd), a potent antitumor nucleoside. Isobutyryloxy group as an efficient anomeric leaving group in the Vorbrüggen glycosylation reaction

  摘要：

  A practical synthetic route to the antitumor nucleoside, 1-(3-C-ethynyl-beta-D-ribo-pentofuranosyl)cytosine (ECyd, 1) from 1,2-O-isopropylidene-D-xylofuranose (3) has been developed. Since most of the compounds were obtained as crystals, the target ECyd was prepared without any chromatographic purification in 31% overall yield from compound 3. The isobutyryloxy group was found to be an effective leaving group at the anomeric position of the 3-beta-C-ethynyl glycosyl donors in the key Vorbruggen glycosylation reaction. Using a similar procedure without chromatographic purification, the uracil congener EUrd [1-(3-C-ethynyl-beta-D-ribo-pentofuranosyl)uracil (2), which also has a potent antitumor effect, was synthesized from 3 in 39% overall yield. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(01)01249-2
• 作为产物：
  描述：

  三甲基乙炔基硅 、 5-O-(4-chlorobenzoyl)-1,2-O-isopropylidene-D-erythro-pentofuranose03-urose 在 乙基溴化镁 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以91%的产率得到5-O-(4-chlorobenzoyl)-1,2-O-isopropylidene-3-C-[2-(trimethylsilyl)ethynyl]-D-ribo-pentofuranose
  参考文献：
  名称：

  Nucleosides and nucleotides. Part 212: Practical large-scale synthesis of 1-(3-C-ethynyl-β-d-ribo-pentofuranosyl)cytosine (ECyd), a potent antitumor nucleoside. Isobutyryloxy group as an efficient anomeric leaving group in the Vorbrüggen glycosylation reaction

  摘要：

  A practical synthetic route to the antitumor nucleoside, 1-(3-C-ethynyl-beta-D-ribo-pentofuranosyl)cytosine (ECyd, 1) from 1,2-O-isopropylidene-D-xylofuranose (3) has been developed. Since most of the compounds were obtained as crystals, the target ECyd was prepared without any chromatographic purification in 31% overall yield from compound 3. The isobutyryloxy group was found to be an effective leaving group at the anomeric position of the 3-beta-C-ethynyl glycosyl donors in the key Vorbruggen glycosylation reaction. Using a similar procedure without chromatographic purification, the uracil congener EUrd [1-(3-C-ethynyl-beta-D-ribo-pentofuranosyl)uracil (2), which also has a potent antitumor effect, was synthesized from 3 in 39% overall yield. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(01)01249-2

文献信息

• D-pentofuranose derivatives and process for preparing the same
  申请人：Taiho Pharmaceutical Co., Ltd.

  公开号：US05880294A1

  公开（公告）日：1999-03-09

  The present invention relates to D-pentofuranose derivatives represented by the following formulas (1) through (4): ##STR1## (wherein A represents a chlorobenzoyl group; R.sup.1 represents a hydrogen atom, an aliphatic lower acyl group, a substituted or unsubstituted benzoyl group; each of X and Y represents a lower alkyl group; Z represents an ethynyl group or tri-lower alkyl silylethynyl group; the sugar moiety in formula (1) represents xylose; and the sugar moiety of each of formulas (3) and (4) represents ribose). The present invention also relates to a process for preparing the compound (2) characterized by oxidizing the compound of formula (1) with a hypochlorite in the presence of a catalytic amount of 2,2,6,6-tetramethylpiperidinoxy compound, and these compounds are useful as intermediates in the synthesis of 3'-C-substituted ribonucleoside derivatives having excellent antitumor activities.

  本发明涉及通式(1)至(4)所示的D-戊呋喃糖衍生物：##STR1##（其中A代表氯苯甲酰基；R1代表氢原子、低级脂肪族酰基、取代或未取代的苯甲酰基；X和Y各自代表低级烷基；Z代表乙炔基或三低级烷基硅乙炔基；式(1)中的糖部分代表木糖；式(3)和(4)中的糖部分各自代表核糖）。本发明还涉及制备化合物(2)的方法，其特征在于在2,2,6,6-四甲基哌啶氧基化合物催化量的存在下，用次氯酸盐氧化式(1)的化合物，这些化合物作为合成具有优异抗肿瘤活性的3'-C-取代的核糖核苷衍生物的中间体是有用的。
• Nucleosides and nucleotides. Part 212: Practical large-scale synthesis of 1-(3-C-ethynyl-β-d-ribo-pentofuranosyl)cytosine (ECyd), a potent antitumor nucleoside. Isobutyryloxy group as an efficient anomeric leaving group in the Vorbrüggen glycosylation reaction
  作者：Makoto Nomura、Tsutomu Sato、Masato Washinosu、Motoaki Tanaka、Tetsuji Asao、Satoshi Shuto、Akira Matsuda

  DOI：10.1016/s0040-4020(01)01249-2

  日期：2002.2

  A practical synthetic route to the antitumor nucleoside, 1-(3-C-ethynyl-beta-D-ribo-pentofuranosyl)cytosine (ECyd, 1) from 1,2-O-isopropylidene-D-xylofuranose (3) has been developed. Since most of the compounds were obtained as crystals, the target ECyd was prepared without any chromatographic purification in 31% overall yield from compound 3. The isobutyryloxy group was found to be an effective leaving group at the anomeric position of the 3-beta-C-ethynyl glycosyl donors in the key Vorbruggen glycosylation reaction. Using a similar procedure without chromatographic purification, the uracil congener EUrd [1-(3-C-ethynyl-beta-D-ribo-pentofuranosyl)uracil (2), which also has a potent antitumor effect, was synthesized from 3 in 39% overall yield. (C) 2002 Elsevier Science Ltd. All rights reserved.