4,6-di-O-tert-butyldimethylsilyl-3-deoxy-D-glucal | 79999-50-1

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 4,6-di-O-tert-butyldimethylsilyl-3-deoxy-D-glucal
• 英文别名: tert-butyl-[[(2R,3S)-3-[tert-butyl(dimethyl)silyl]oxy-3,4-dihydro-2H-pyran-2-yl]methoxy]-dimethylsilane
• CAS: 79999-50-1
• 化学式: C₁₈H₃₈O₃Si₂
• 分子量: 358.669
• InChiKey: DPJGZDBVSNCYGU-JKSUJKDBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  23
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4,6-di-O-tert-butyldimethylsilyl-3-deoxy-D-glucal 在 pyridinium chlorochromate 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以71%的产率得到4,6-di-O-tert-butyldimethylsilyl-2,3-dideoxy-D-erythro-hexono-1,5-lactone
  参考文献：
  名称：

  A convenient, one-step oxidation of glycals to lactones using pyridinium chlorochromate

  摘要：

  DOI：

  10.1016/s0008-6215(00)87151-7
• 作为产物：
  描述：

  叔丁基二甲基氯硅烷 、 3,4,6-三-O-甲基-D-葡萄糖醛 生成 4,6-di-O-tert-butyldimethylsilyl-3-deoxy-D-glucal
  参考文献：
  名称：

  Preparation and use of lithiated glycals: vinylic deprotonation versus tin-lithium exchange from 1-tributylstannyl glycals1

  摘要：

  DOI：

  10.1016/s0040-4039(00)85432-5

文献信息

• Simple oxidation of 3-O-silylated glycals: application in deblocking 3-O-protected glycals
  作者：Andreas Kirschning、Ulrike Hary、Claus Plumeier、Monika Ries、Lars Rose

  DOI：10.1039/a807479h

  日期：——

  A high yielding allylic oxidation of 3-O-silylated glycals 5–10 with the reagent system PhI(OAc)2–TMSN3 is presented. The iodine(III) species generated under these conditions is a lot more effective for generating carbohydrate-derived 3-trialkylsiloxy-2,3-dihydro-4H-pyran-4-ones 11–15 than is [hydroxy(tosyloxy)iodo]benzene, the Koser reagent. Even disaccharide 9 containing the oxidation-labile phenylseleno group is smoothly oxidized to the corresponding enone 15. The hypervalent azido iodine reagent is complementary to the Koser reagent, because 3-O-benzylated or -acylated glycals cannot be oxidized. When the iodine(III)-mediated oxidation of 3-O-silylated or -benzylated glycals is followed by a reduction step, the formal 3-O-deblocking of glycals is achieved. In particular, the Luche reduction of enones obtained from the oxidation of lyxo-configured glycals 24 and 26 is highly selective and exclusively affords the corresponding lyxo-configured glycals 28 and 30. In some cases, these products can be transformed under Mitsunobu conditions into glycals with inverted configuration at C-3 in moderate yield.

  提出了一种高产率的3-O-硅烷化糖醇5–10的烯丙氧化反应，使用的试剂系统为PhI(OAc)2–TMSN3。在这些条件下生成的碘(III)物种相比于Koser试剂[羟基(托芳基羟基)碘]苯，更有效地生成以碳水化合物为基础的3-三烷基硅氧基-2,3-二氢-4H-吡喃-4-酮11–15。即使是含有易氧化的苯基硒基的二糖9，也能平稳地氧化成相应的烯酮15。超价的叠氮碘试剂与Koser试剂互补，因为3-O-苄基化或-酰基化的糖醇无法被氧化。当3-O-硅烷化或-苄基化的糖醇进行碘(III)介导的氧化后再进行还原步骤时，可以实现糖醇的形式性3-O-去堵功能。特别是，从lyxo构型的糖醇24和26氧化得到的烯酮进行Luche还原反应时，选择性极高，专门生成相应的lyxo构型的糖醇28和30。在某些情况下，这些产物可以在Mitsunobu条件下转化为C-3配置反转的糖醇，且产率适中。
• Radical cyclization on carbohydrate pyranosides: A controlled formation of functionalized ring-fused bicyclic acetals
  作者：Catherine Audin、Jean-Marc Lancelin、Jean-Marie Beau

  DOI：10.1016/s0040-4039(00)82155-3

  日期：——

  Cis-fused chiral bicyclic acetals are readily prepared from glycals in a two-step procedure via the tri-n-butylstanne-mediated cyclization of simple ω-unsaturated glycosides of 2-bromo- 2-deoxy-glycopyranosides.

  顺式稠合的手性双环缩醛很容易在两步过程中通过三正丁基锡介导的2-溴-2-脱氧糖吡喃糖苷的简单ω-不饱和糖苷的三正丁基锡介导的环化作用由糖制备。
• AUDIN, CATHERINE;LANCELIN, JEAN-MARC;BEAU, JEAN-MARIE, TETRAHEDRON LETT., 29,(1988) N 30, C. 3691-3694
  作者：AUDIN, CATHERINE、LANCELIN, JEAN-MARC、BEAU, JEAN-MARIE

  DOI：——

  日期：——
• A convenient, one-step oxidation of glycals to lactones using pyridinium chlorochromate
  作者：Patrick Rollin、Pierre Sinaÿ

  DOI：10.1016/s0008-6215(00)87151-7

  日期：1981.12
• Preparation and use of lithiated glycals: vinylic deprotonation versus tin-lithium exchange from 1-tributylstannyl glycals1
  作者：Patrick Lesimple、Jean-Marie Beau、Guy Jaurand、Pierre Sinaÿ

  DOI：10.1016/s0040-4039(00)85432-5

  日期：1986.1