2,5,6-trideoxy-D-erythro-hexofuranose

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,5,6-trideoxy-D-erythro-hexofuranose
• 英文别名: 2-deoxy-D-erythro-ribose；(4S,5R)-5-ethyloxolane-2,4-diol
• 化学式: C₆H₁₂O₃
• 分子量: 132.159
• InChiKey: YXRBVLUOCLPFAB-YRZWDFBDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  49.7
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2,5,6-trideoxy-D-erythro-hexofuranose 在 吡啶 、 咪唑 、 盐酸 、 4-二甲氨基吡啶 、 N-溴代丁二酰亚胺(NBS) 、 lithium hydroxide monohydrate 、 偶氮二甲酸二异丙酯 、 三氟化硼乙醚 、 四丁基氟化铵 、 氨 、 丁胺氢碘酸盐 、 三乙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 甲醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 265.0h， 生成 4-氨基-1-[(4S,5R)-4-羟基-5-(羟基甲基)四氢噻吩-2-基]嘧啶-2-酮
  参考文献：
  名称：

  用苄基取代的 2-deoxy-1,4-dithio-D-erythro-pentofuranosides 开发 β-选择性糖基化反应：实现 4'-Thio-2'-deoxycytidine (T-dCyd) 和 5 的实际多克合成-aza-4'-thio-2'-deoxycytidine (aza-T-dCyd) 支持临床开发

  摘要：

  摘要 长期以来，缺乏与 2-deoxy-1,4-dithio-D-erythro-pentofuranosides 进行直接 β-选择性糖基化反应的有效方法一直是多克合成 4'-thio-2 的重要障碍。 '-脱氧核苷。此外，先前报道的制备适当取代的 2-deoxy-1,4-dithio-D-erythro-pentofuranosides 的方法已证明对大规模合成存在问题。为了解决这些问题，我们在本文中描述了对先前报道的方法的修改和优化，以方便地大规模合成苄基取代的 2-脱氧-1,4-二硫代-D-赤型-戊呋喃糖苷。此外，我们描述了苄基取代的 2-deoxy-1 的 β-选择性糖基化反应的反应条件的发展，4-dithio-D-erythro-pentofuranosides 与 N4-benzoylcytosine 和 5-aza-cytosine，使临床候选物 4'-thio-2'-deoxycytidine

  DOI：

  10.1080/15257770.2020.1832694
• 作为产物：
  描述：

  2-hydroxybutanal 、 乙醛 在 乙二胺四乙酸 作用下， 以 水 为溶剂， 反应 48.0h， 以18%的产率得到2,5,6-trideoxy-D-erythro-hexofuranose
  参考文献：
  名称：

  Deoxyribose 5-phosphate aldolase as a catalyst in asymmetric aldol condensation

  摘要：

  This paper describes the substrate specificity and synthetic utility of deoxyribose-5-phosphate aldolase (DERA, EC 4.1.2.4). Eight donors and 20 acceptors have been tested as substrates. In addition to acetaldehyde, propanal, acetone, and fluoroacetone have been used to condense with a number of acceptor aldehydes. Thirteen aldol products have been prepared and characterized. A new stereogenic center with 3(S) configuration is formed when acetaldehyde, fluoroacetone, or acetone is used as a donor substrate. With propanal, two new stereogenic centers are formed with 2(R) and 3(S) configurations. The acceptor substrates have very little structural requirements. The 2-hydroxyaldehydes appear to react the fastest, and the D-isomers are better substrates than the L-isomers. The stereospecificity is absolute regardless of the chirality of 2-hydroxyaldehydes. The aldol reactions thus follow the Cram-Felkin mode of attack for D-substrates and anti-Cram-Felkin mode of attack for L-substrates.

  DOI：

  10.1021/ja00028a050

文献信息

• Deoxyribose 5-phosphate aldolase as a catalyst in asymmetric aldol condensation
  作者：Lihren Chen、David P. Dumas、Chi Huey Wong

  DOI：10.1021/ja00028a050

  日期：1992.1

  This paper describes the substrate specificity and synthetic utility of deoxyribose-5-phosphate aldolase (DERA, EC 4.1.2.4). Eight donors and 20 acceptors have been tested as substrates. In addition to acetaldehyde, propanal, acetone, and fluoroacetone have been used to condense with a number of acceptor aldehydes. Thirteen aldol products have been prepared and characterized. A new stereogenic center with 3(S) configuration is formed when acetaldehyde, fluoroacetone, or acetone is used as a donor substrate. With propanal, two new stereogenic centers are formed with 2(R) and 3(S) configurations. The acceptor substrates have very little structural requirements. The 2-hydroxyaldehydes appear to react the fastest, and the D-isomers are better substrates than the L-isomers. The stereospecificity is absolute regardless of the chirality of 2-hydroxyaldehydes. The aldol reactions thus follow the Cram-Felkin mode of attack for D-substrates and anti-Cram-Felkin mode of attack for L-substrates.
• The development of β-selective glycosylation reactions with benzyl substituted 2-deoxy-1,4-dithio-D-<i>erythro</i>-pentofuranosides: enabling practical multi-gram syntheses of 4'-Thio-2'-deoxycytidine (T-dCyd) and 5-aza-4’-thio-2’-deoxycytidine (aza-T-dCyd) to support clinical development
  作者：Donn G. Wishka、Omar D. Lopez、Vladimir F. Rudchenko、Guangfei Huang、Robert Bahde、Vineet Kumar、Sergiy M. Denysenko、Lianhao Zhang、Mianji Zhang、Beverly A. Teicher、Joel Morris

  DOI：10.1080/15257770.2020.1832694

  日期：2021.1.2

  perform direct β-selective glycosylation reactions with 2-deoxy-1,4-dithio-D-erythro-pentofuranosides has long been a significant stumbling block for the multi-gram synthesis of 4’-thio-2’-deoxy nucleosides. In addition, previously reported methods for the preparation of appropriately substituted 2-deoxy-1,4-dithio-D-erythro-pentofuranosides have proven problematic for large scale synthesis. To address

  摘要 长期以来，缺乏与 2-deoxy-1,4-dithio-D-erythro-pentofuranosides 进行直接 β-选择性糖基化反应的有效方法一直是多克合成 4'-thio-2 的重要障碍。 '-脱氧核苷。此外，先前报道的制备适当取代的 2-deoxy-1,4-dithio-D-erythro-pentofuranosides 的方法已证明对大规模合成存在问题。为了解决这些问题，我们在本文中描述了对先前报道的方法的修改和优化，以方便地大规模合成苄基取代的 2-脱氧-1,4-二硫代-D-赤型-戊呋喃糖苷。此外，我们描述了苄基取代的 2-deoxy-1 的 β-选择性糖基化反应的反应条件的发展，4-dithio-D-erythro-pentofuranosides 与 N4-benzoylcytosine 和 5-aza-cytosine，使临床候选物 4'-thio-2'-deoxycytidine