3-O-benzyl-1,2-O-isopropylidene-β-D-psicopyranose | 872345-40-9

• 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: 3-O-benzyl-1,2-O-isopropylidene-β-D-psicopyranose
• 英文别名: (5S,6R,7R,8R)-2,2-dimethyl-6-phenylmethoxy-1,3,10-trioxaspiro[4.5]decane-7,8-diol
• CAS: 872345-40-9
• 化学式: C₁₆H₂₂O₆
• 分子量: 310.347
• InChiKey: ZKRXJONPNLPKEN-KQTLUZQSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  77.4
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3-O-benzyl-1,2-O-isopropylidene-β-D-psicopyranose 在 咪唑 、 碘 、 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以56%的产率得到3-O-benzyl-4-deoxy-4-iodo-1,2-O-isopropylidene-β-D-sorbopyranose
  参考文献：
  名称：

  在吡喃糖模板上选择性碘化的受控 Garegg 条件

  摘要：

  在受控的 Garegg 条件下，对位于吡喃糖模板上的邻二醇和连续三醇进行区域选择性和立体选择性碘化。基于 P-D-果糖或吡喃吡喃糖的二醇分别在 C-5 或 C-4 处选择性碘化，以提供 L-山梨糖或 D-塔格托碘醇。相比之下，相关的三醇仅在 C-5 处进行选择性碘化。将该方法应用于 D-葡糖苷和 D-吡喃半乳糖苷导致分别在 C-3 或 C-4 处选择性碘化，以提供 D-allo 或 D-葡糖碘醇。

  DOI：

  10.1002/ejoc.201001325
• 作为产物：
  描述：

  3-O-benzyl-1,2:4,5-di-O-isopropylidene-β-D-psicopyranose 在 溶剂黄146 作用下， 反应 2.0h， 以79%的产率得到3-O-benzyl-1,2-O-isopropylidene-β-D-psicopyranose
  参考文献：
  名称：

  Polyhydroxylated pyrrolidines, III. Synthesis of new protected 2,5-dideoxy-2,5-iminohexitols from d-fructose

  摘要：

  The readily available 3-O-benzoyl-4-O-benzyl-1,2-Oisopi-opylidene-beta-D-fructopyranose (6) was straightforwardly transformed into 5-azido-3-O-benzoyl-4-O-benzyl-5-deoxy-1,2-O-isopropylidene-beta-D-fructopyranose (8), after treatment under modified Garegg's conditions followed by reaction of the resulting 3-O-benzoyl-4-O-benzyl-5-deoxy-5-iodo-1,2-O-isopropylidene-alpha-L-sorbopyranose (7) with lithium azide in DMF O-debenzoylation at C(3) in 8, followed by oxidation and reduction caused the inversion of the configuration to afford the corresponding beta-D-psicopyranose derivative 11 that was transformed into the related 3,4-di-O-benzyl derivative 12. Cleavage of the acetonide of 12 to give 13 followed by O-tert-butyldiphenylsilylation afforded a resolvable mixture of 14 and 15. Compound 14 was transformed into (2R,3R,4S,5R)- (17) and (2R,3R,4S,5S)-3,4-dibenzyloxy-2',5'-di-O-tert-butyldiphenylsilyl-2,5-bis(hydroxymethyl)pyrrolidine (18) either by a tandem Staudinger/intramolecular aza-Wittig process and reduction of the resulting intermediate 2 only into 18 by a high stereoselective catalytic hydrogenation. When 15 was subjected to the same protocol, (2S,3S,4R,5R)- (21) and (2R,3S,4R,5R)-3,4-dibenzyloxy-2'-O-tert-butyldiphenylsilyl-2,5-bis(hydroxymethyl)pyrrolidine (22) were obtained, respectively. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.09.043

文献信息

• Diphenylphosphinoylethylidene (DPE) acetals: an alternative protective strategy in glycochemistry
  作者：Leonardo Pellizzaro、Arnaud Tatibouët、Fabrizio Fabris、Patrick Rollin、Ottorino De Lucchi

  DOI：10.1016/j.tetlet.2008.10.111

  日期：2009.1

  Diphenylphoshinoylethyne reacts with diols under basic conditions to produce cycloacetalic phosphine oxides. The reaction appears to be general and particularly effective with carbohydrate derivatives. The 2-(diphenylplioshinoyl)ethylidene (DPE) acetals produced are stable in acidic media while they can be cleaved under reductive and/or basic conditions: base-catalyzed transacetalization is a method of choice for their mild and effective deprotection. (C) 2008 Published by Elsevier Ltd.
• Selective iodination of vicinal cis-diols on ketopyranose templates
  作者：Ana Catarina Simao、Arnaud Tatibouët、Amelia P. Rauter、Patrick Rollin

  DOI：10.1016/j.tetlet.2010.06.107

  日期：2010.9

  A regio- and stereoselective iodination has been performed on vicinal diols located on ketopyranose templates using the controlled-Garegg conditions. 3-O-Benzy1-1,2-O-isopropylidene-beta-D-fructo- or psicopyranoses (1 or 4) were selectively iodinated, respectively, at C-5 or C-4 of the ketoses to afford the L-sorbo or D-sorbo iodohydrins. (C) 2010 Elsevier Ltd. All rights reserved.
• Controlled Garegg Conditions for Selective Iodination on Pyranose Templates
  作者：Ana-Catarina Simao、Sandrina Silva、Amelia P. Rauter、Patrick Rollin、Arnaud Tatibouët

  DOI：10.1002/ejoc.201001325

  日期：2011.4

  Regio- and stereoselective iodinations under controlled Garegg conditions were performed on vicinal diols and contiguous triols located on pyranose templates. P- D -Fructo- or psicopyranose-based diols were selectively iodinated at C-5 or C-4, respectively, to afford the L -sorbo or D -tagato iodohydrins. In contrast, the related triols only underwent selective iodination at C-5. Application of the

  在受控的 Garegg 条件下，对位于吡喃糖模板上的邻二醇和连续三醇进行区域选择性和立体选择性碘化。基于 P-D-果糖或吡喃吡喃糖的二醇分别在 C-5 或 C-4 处选择性碘化，以提供 L-山梨糖或 D-塔格托碘醇。相比之下，相关的三醇仅在 C-5 处进行选择性碘化。将该方法应用于 D-葡糖苷和 D-吡喃半乳糖苷导致分别在 C-3 或 C-4 处选择性碘化，以提供 D-allo 或 D-葡糖碘醇。
• Polyhydroxylated pyrrolidines, III. Synthesis of new protected 2,5-dideoxy-2,5-iminohexitols from d-fructose
  作者：Isidoro Izquierdo、María T. Plaza、Miguel Rodríguez、Francisco Franco、Alicia Martos

  DOI：10.1016/j.tet.2005.09.043

  日期：2005.12

  The readily available 3-O-benzoyl-4-O-benzyl-1,2-Oisopi-opylidene-beta-D-fructopyranose (6) was straightforwardly transformed into 5-azido-3-O-benzoyl-4-O-benzyl-5-deoxy-1,2-O-isopropylidene-beta-D-fructopyranose (8), after treatment under modified Garegg's conditions followed by reaction of the resulting 3-O-benzoyl-4-O-benzyl-5-deoxy-5-iodo-1,2-O-isopropylidene-alpha-L-sorbopyranose (7) with lithium azide in DMF O-debenzoylation at C(3) in 8, followed by oxidation and reduction caused the inversion of the configuration to afford the corresponding beta-D-psicopyranose derivative 11 that was transformed into the related 3,4-di-O-benzyl derivative 12. Cleavage of the acetonide of 12 to give 13 followed by O-tert-butyldiphenylsilylation afforded a resolvable mixture of 14 and 15. Compound 14 was transformed into (2R,3R,4S,5R)- (17) and (2R,3R,4S,5S)-3,4-dibenzyloxy-2',5'-di-O-tert-butyldiphenylsilyl-2,5-bis(hydroxymethyl)pyrrolidine (18) either by a tandem Staudinger/intramolecular aza-Wittig process and reduction of the resulting intermediate 2 only into 18 by a high stereoselective catalytic hydrogenation. When 15 was subjected to the same protocol, (2S,3S,4R,5R)- (21) and (2R,3S,4R,5R)-3,4-dibenzyloxy-2'-O-tert-butyldiphenylsilyl-2,5-bis(hydroxymethyl)pyrrolidine (22) were obtained, respectively. (c) 2005 Elsevier Ltd. All rights reserved.