1,2-O-isopropylidene-5-O-(tert-butyldimethylsilyl)-3-C-phenylethynyl-α-D-ribofuranose | 896130-08-8

• 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-5-O-(tert-butyldimethylsilyl)-3-C-phenylethynyl-α-D-ribofuranose
• 英文别名: (3aR,5R,6R,6aR)-5-[[tert-butyl(dimethyl)silyl]oxymethyl]-2,2-dimethyl-6-(2-phenylethynyl)-5,6a-dihydro-3aH-furo[2,3-d][1,3]dioxol-6-ol
• CAS: 896130-08-8
• 化学式: C₂₂H₃₂O₅Si
• 分子量: 404.579
• InChiKey: SNXLAFXZVXGVQB-VQQMMKBISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.67
• 重原子数：
  28
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  57.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1,2-O-isopropylidene-5-O-(tert-butyldimethylsilyl)-3-C-phenylethynyl-α-D-ribofuranose 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以80%的产率得到1,2-O-isopropylidene-3-C-phenylethynyl-α-D-ribofuranose
  参考文献：
  名称：

  Palladium mediated cycloisomerization of sugar alkynols: synthesis of cyclic enol-ethers and spiroketals

  摘要：

  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.

  DOI：

  10.1016/j.tetlet.2006.03.143
• 作为产物：
  描述：

  5-O-(tert-butyldimethylsilyl)-1,2-O-isopropylidene-α-D-erythro-pentofuranos-3-ulose 、 lithium phenylacetylide 以 四氢呋喃 为溶剂， 以81%的产率得到1,2-O-isopropylidene-5-O-(tert-butyldimethylsilyl)-3-C-phenylethynyl-α-D-ribofuranose
  参考文献：
  名称：

  Palladium mediated cycloisomerization of sugar alkynols: synthesis of cyclic enol-ethers and spiroketals

  摘要：

  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.

  DOI：

  10.1016/j.tetlet.2006.03.143

文献信息

• Target cum flexibility: synthesis of C(3′)-spiroannulated nucleosides
  作者：Mangesh P. Dushing、C.V. Ramana

  DOI：10.1016/j.tetlet.2011.06.100

  日期：2011.9

  report a simple strategy for the synthesis of a collection of C(3′)-spirodihydroisobenzo-furannulated nucleosides featuring a [2+2+2]-cyclotrimerization as the key reaction. The cyclotrimerization reactions are facile with the unprotected nucleosides having a diyne unit. When both alkynes of the diyne are terminal, the regioselectivity is poor. However, when one of the terminal alkynes is additionally

  我们报告了一个简单的策略，用于合成以（2 + 2 + 2）-环三聚为关键反应的C（3'）-螺二氢异苯并呋喃核苷的集合。环三聚反应容易与具有二炔单元的未保护的核苷一起进行。当二炔的两个炔都是末端时，区域选择性差。然而，当末端炔烃之一被另外取代时，环三聚是高度非对映选择性的。由于关键的双环环化是最后一步，因此该策略在炔烃方面提供了灵活性，因此适合合成聚焦的小分子文库。
• Spiroannulated Nucleosides and Process for the Preparation Thereof
  申请人：Chepuri Venkata Ramana

  公开号：US20130289266A1

  公开（公告）日：2013-10-31

  We claim a simple strategy for the synthesis of a collection of C(3′)-spirodihydroisobenzo- furannulated and C(3′)-spirodihydroisobenzo-furannulated nucleosides featuring a [2+2+2]-cyclotrimerization as the key reaction. The cyclotrimerization reactions are facile with the unprotected nucleosides having a diyne unit. When both alkynes of the diyne are terminal, the regioselectivity is poor. However, when one of the terminal alkynes is additionally substituted, the cyclotrimerizations are highly diaste reoselective. Since the key bicycloannulation is the final step, this strategy provides flexibility in terms of the alkynes and is thus amenable for the synthesis of a focussed small molecule library.

  我们提出了一种简单的合成策略，用于合成一系列C(3′)-螺二氢异苯并呋喃和C(3′)-螺二氢异苯并呋喃核苷，其特点是[2+2+2]-环三聚化反应作为关键反应。未保护的核苷具有二炔基团，环三聚化反应是容易进行的。当二炔基团的两个炔基都是末端时，区域选择性较差。然而，当一个末端炔基另外被取代时，环三聚化反应具有很高的立体选择性。由于关键的双环融合是最后一步，这种策略在炔烃方面提供了灵活性，因此适合用于合成一个专注的小分子库。
• [EN] SPIROANNULATED NUCLEOSIDES AND PROCESS FOR THE PREPARATION THEREOF<br/>[FR] NUCLÉOSIDES SPIROANNELÉS ET LEUR PROCÉDÉ DE PRÉPARATION ASSOCIÉ
  申请人：COUNCIL SCIENT IND RES

  公开号：WO2012090155A1

  公开（公告）日：2012-07-05

  We claim a simple strategy for the synthesis of a collection of C(3')-spirodihydroisobenzo- furannulated and C(3')-spirodihydroisobenzo-furannulated nucleosides featuring a [2+2+2]- cyclotrimerization as the key reaction. The cyclotrimerization reactions are facile with the unprotected nucleosides having a diyne unit. When both alkynes of the diyne are terminal, the regioselectivity is poor. However, when one of the terminal alkynes is additionally substituted, the cyclotrimerizations are highly diastereoselective. Since the key bicycloannulation is the final step, this strategy provides flexibility in terms of the alkynes and is thus amenable for the synthesis of a focussed small molecule library.

  我们提出了一种简单的合成策略，用于合成一系列C（3'）-螺二氢异苯并呋喃核苷和C（3'）-螺二氢异苯并呋喃核苷，其中的[2+2+2]环三聚反应是关键反应。未保护的核苷具有diyne基团，因此环三聚反应容易进行。当diyne的两个炔基都是末端炔基时，区域选择性较差。然而，当其中一个末端炔基另外还有取代基时，环三聚反应高度对映选择性。由于关键的双环化是最后一步，因此这种策略在炔基方面具有灵活性，因此适用于合成集中的小分子库。
• 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.