1,2-O-isopropylidene-3-C-ethynyl-α-D-allofuranose | 97694-32-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,2-O-isopropylidene-3-C-ethynyl-α-D-allofuranose
• 英文别名: (1R)-1-[(3aR,5R,6R,6aR)-6-ethynyl-6-hydroxy-2,2-dimethyl-5,6a-dihydro-3aH-furo[2,3-d][1,3]dioxol-5-yl]ethane-1,2-diol
• CAS: 97694-32-1
• 化学式: C₁₁H₁₆O₆
• 分子量: 244.244
• InChiKey: ZOXXXYOBROYBJE-ZBGLXGBJSA-N

物化性质

• 沸点：
  425.7±45.0 °C(Predicted)
• 密度：
  1.41±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -1.1
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  88.4
• 氢给体数：
  3
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1,2-O-isopropylidene-3-C-ethynyl-α-D-allofuranose 在 吡啶 、 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 sodium periodate 、 N,O-双三甲硅基乙酰胺 、 三氟甲磺酸三甲基硅酯 、 氨 、 三氟乙酸 作用下， 以 甲醇 、 水 、 乙腈 为溶剂， 反应 142.5h， 生成 乙炔基胞苷
  参考文献：
  名称：

  Synthesis and biological evaluation of nucleobase-modified analogs of the anticancer compounds 3′-C-ethynyluridine (EUrd) and 3′-C-ethynylcytidine (ECyd)

  摘要：

  A series of nucleobase-modified analogs of the anticancer compounds 3'-C-ethynyluridine (EUrd) and 3'-C-ethynylcytidine (ECyd) were designed to overcome the strict substrate specificity of the activating uridine-cytidine kinase. EUrd, ECyd and target nucleosides were obtained using a short convergent synthetic route utilizing diacetone-alpha-D -glucose as starting material. 5-lodo -substituted EUrd was the most potent inhibitor among the novel nucleobase-modified analogs in in vitro assays against human adenocarcinoma breast and prostate cancer cells with IC50 values down to 35 nM. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmc.2004.11.054
• 作为产物：
  描述：

  3-C-ethynyl-1,2:5,6-di-O-isopropylidene-D-glucofuranoside 在 溶剂黄146 作用下， 反应 2.0h， 以93%的产率得到1,2-O-isopropylidene-3-C-ethynyl-α-D-allofuranose
  参考文献：
  名称：

  Synthesis and Conformational Analysis of A Novel Type of Spin Labelled Bicyclonucleoside Based on A Tetrahydrofurano[2,3-c]Pyrrolidine Sugar Skeleton

  摘要：

  Bicyclonucleosides bearing a 5-deoxy-5-N-hydroxyamino-3,N-5-(1,1-ethano)-beta-D-furanosyl sugar moiety (15-18) have been prepared by glycosidation of the corresponding bicyclosugars obtained via an intramolecular reverse Cope elimination. The configuration of the asymmetric carbon of the 1,1-ethano bridge is the most important factor directing the conformation of the N-hydroxypyrrolidine ring and its invertomers ratio as shown by variable temperature H NMR experiments.

  DOI：

  10.1080/07328319808004218

文献信息

• Synthesis and biological evaluation of branched and conformationally restricted analogs of the anticancer compounds 3′-C-ethynyluridine (EUrd) and 3′-C-ethynylcytidine (ECyd)
  作者：Patrick J. Hrdlicka、Nicolai K. Andersen、Jan S. Jepsen、Flemming G. Hansen、Kim F. Haselmann、Claus Nielsen、Jesper Wengel

  DOI：10.1016/j.bmc.2005.01.029

  日期：2005.4

  The synthesis of branched and conformationally restricted analogs of the anticancer nucleosides 3'-C-ethynyluridine (EUrd) and 3'-C-ethynylcytidine (ECyd) is presented. Molecular modeling and (1)H NMR coupling constant analysis revealed that the furanose rings of all analogs except the LNA analog are conformationally biased towards South conformation, and are thus mimicking the structure of ECyd. All

  提出了抗癌核苷3'-C-乙炔基尿苷（EUrd）和3'-C-乙炔基胞苷（ECyd）的分支和构象受限的类似物的合成。分子建模和（1）1 H NMR偶合常数分析表明，除LNA类似物外，所有类似物的呋喃糖环均在构象上偏向South构象，因此模仿ECyd的结构。所有靶标核苷都没有抗HIV或抗癌活性。
• Rearrangements of Haloalkynol Derivatives of Glucofuranose
  作者：Maureen Blandino、Edward McNelis

  DOI：10.1021/ol026422q

  日期：2002.10.1

  Bromoalkynol derivatives of diacetone glucose undergo rearrangements to dihaloenol ethers contained in furo[3,4-b]furan cores when treated with halonium-producing reagents. [reaction: see text]

  当用产ha试剂处理时，双丙酮葡萄糖的溴炔醇衍生物会重排为呋喃[3,4-b]呋喃核中所含的二卤代烯醇醚。[反应：看文字]
• Strategies and tactics for free radical carbocyclization: synthesis of polyfunctionalized cyclopentanoid molecules from carbohydrates
  作者：José Marco-Contelles、Pilar Ruiz、Luis Martínez、Angeles Martínez-Grau

  DOI：10.1016/s0040-4020(01)81837-8

  日期：1993.7

  The tributyltin hydride + azobisisobutyronitrile (AIBN) mediated free radical carbocyclization of precursors 1-9, 48 and 49 is described. The resulting carbocycles have been obtained in moderate yield and good diastereoselectivity. These polyfunctionalized, enantiomerically pure cyclopentane derivatives are useful intermediates for further manipulation.
• The influence of electronic factors on palladium-mediated cycloisomerization: a systematic investigation of competitive 5-exo-dig versus 6-endo-dig cyclizations of sugar alkynols
  作者：C.V. Ramana、Rosy Mallik、Rajesh G. Gonnade

  DOI：10.1016/j.tet.2007.10.072

  日期：2008.1

  Pd-mediated cycloisomerization of 3-C-alkynyl-allo- and ribofuranose derivatives was investigated in detail to understand the influence of electronic factors on the regioselectivity in ring closure reaction. The reactions in general are influenced by the electronic nature of the substituent on the alkyne unit. A preference for endo-dig cyclization over exo-dig is noted, if the alkynyl substituent is not sufficiently electron withdrawing, (c) 2007 Elsevier Ltd. All rights reserved.
• Palladium mediated cycloisomerization of sugar alkynols: synthesis of cyclic enol-ethers and spiroketals
  作者：C.V. Ramana、Rosy Mallik、Rajesh G. Gonnade、Mukund K. Gurjar

  DOI：10.1016/j.tetlet.2006.03.143

  日期：2006.5

  Functionalized bicyclic enol-ethers and spiroketals are prepared by Pd catalyzed cycloisomerization of 3-C-alkynylfuranosyl derivatives. Cycloisomerization of differently substituted alkyne derivatives revealed a preference for 6-endo-dig cyclization over 5-exo-dig if the substituent is not sufficiently electron withdrawing. The scope of these cycloisomerizations has been further extended by integrating with conjugate addition. (c) 2006 Elsevier Ltd. All rights reserved.