1,2:5,6-di-O-isopropylidene-3-C-phenylethynyl-α-D-allofuranose | 56998-53-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,2:5,6-di-O-isopropylidene-3-C-phenylethynyl-α-D-allofuranose
• 英文别名: (3aR,5R,6R,6aR)-5-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-6-(2-phenylethynyl)-5,6a-dihydro-3aH-furo[2,3-d][1,3]dioxol-6-ol
• CAS: 56998-53-9
• 化学式: C₂₀H₂₄O₆
• 分子量: 360.407
• InChiKey: MKDSKMXPNHOWNQ-ISIBIEBGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  26
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  66.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1,2:5,6-di-O-isopropylidene-3-C-phenylethynyl-α-D-allofuranose 在 硫酸 作用下， 以 甲醇 为溶剂， 反应 15.0h， 以70%的产率得到1,2-O-isopropylidene-3-C-phenylethynyl-α-D-allofuranose
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1016/j.tet.2007.10.072
• 作为产物：
  描述：

  1,2:5,6-二-o-异亚丙基-alpha-d-ribo-3-己呋喃核糖 、 lithium phenylacetylide 以 四氢呋喃 、 正己烷 为溶剂， 反应 4.0h， 生成 1,2:5,6-di-O-isopropylidene-3-C-phenylethynyl-α-D-allofuranose
  参考文献：
  名称：

  衍生自二-O-异亚丙基戊基呋喃糖和O-异亚丙基戊基呋喃糖的叔醇的氟化

  摘要：

  已经研究了衍生自二-O-异亚丙基戊基呋喃糖和1,2- O-异亚丙基戊基呋喃糖的各种叔醇的脱羟基氟化的立体和区域选择性。使用DAST和PFPDEA（1,1,3,3,3-五氟丙烯-二乙胺加合物）作为氟化试剂已经完成了反应。烯丙基醇2a的脱羟基氟化已经发生，其构型和烯丙基重排颠倒，导致两个手性区域异构体6a和7a。2b的类似反应产生了烯丙基手性氟化物7b作为唯一产物。如果是苯乙炔，苯乙烯基和苯甲醇3a /在图3b-5a / 5b中，已经获得了单个非对映异构体8a / 8b-10a / 10b。另外，已经讨论了在氟化过程中1，2- O-取代基作用参与碳正离子稳定化。

  DOI：

  10.1016/j.jfluchem.2011.07.001

文献信息

• 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.
• 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.
• Fluorination of tertiary alcohols derived from di-O-isopropylidenehexofuranose and O-isopropylidenepentofuranose
  作者：Magdalena Rapp、Monika Bilska、Henryk Koroniak

  DOI：10.1016/j.jfluchem.2011.07.001

  日期：2011.12

  The stereo- and regioselectivity of the dehydroxyfluorination of various tertiary alcohols derived from di-O-isopropylidenehexofuranose and 1,2-O-isopropylidenepentofuranose has been studied. Reactions have been accomplished using DAST and PFPDEA (1,1,3,3,3-pentafluoropropene-diethylamine adduct) as fluorinating reagents. Dehydroxyfluorination of allylic alcohol 2a has occurred with an inversion of

  已经研究了衍生自二-O-异亚丙基戊基呋喃糖和1,2- O-异亚丙基戊基呋喃糖的各种叔醇的脱羟基氟化的立体和区域选择性。使用DAST和PFPDEA（1,1,3,3,3-五氟丙烯-二乙胺加合物）作为氟化试剂已经完成了反应。烯丙基醇2a的脱羟基氟化已经发生，其构型和烯丙基重排颠倒，导致两个手性区域异构体6a和7a。2b的类似反应产生了烯丙基手性氟化物7b作为唯一产物。如果是苯乙炔，苯乙烯基和苯甲醇3a /在图3b-5a / 5b中，已经获得了单个非对映异构体8a / 8b-10a / 10b。另外，已经讨论了在氟化过程中1，2- O-取代基作用参与碳正离子稳定化。