(2R,3S,6S)-2-((tert-butyldimethylsilyloxy)methyl)-6-methoxy-3,6-dihydro-2H-pyran-3-ol | 108274-95-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: (2R,3S,6S)-2-((tert-butyldimethylsilyloxy)methyl)-6-methoxy-3,6-dihydro-2H-pyran-3-ol
• 英文别名: methyl α-D-6-O-t-butyldimethylsilyl-2,3-dideoxyhex-2-enoerythropyranoside
• CAS: 108274-95-9
• 化学式: C₁₃H₂₆O₄Si
• 分子量: 274.433
• InChiKey: MMEZMCZTWHURIC-TUAOUCFPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  18.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  47.92
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (2R,3S,6S)-2-((tert-butyldimethylsilyloxy)methyl)-6-methoxy-3,6-dihydro-2H-pyran-3-ol 在 4-二甲氨基吡啶 、 Amberlite IRA-900 in azide form 、 三乙胺 作用下， 以 乙酸乙酯 、 苯 为溶剂， 反应 5.0h， 生成 methyl α-D-2-azido-6-O-t-butyldimethylsilyl-2,3,4-trideoxyhex-3-enoglyceropyranoside
  参考文献：
  名称：

  Steric constraints against [3,3]-sigmatropic rearrangement of allylic azides. A convenient approach to β-l-4-aminopent-2-enoglyceropyranosides

  摘要：

  Starting from alkyl alpha -D-4-O-methanesulphonylpent-2-enoglyceropyranosides 13a-c, nucleophilic substitution carried out with polymer-supported azide ion led to regioisomeric mixtures of the azides 14a-c and 15a-c. An analogous result, due to a [3,3]-sigmatropic rearrangement, was observed starting from methyl alpha -D-hex-2-enoerythropyranoside derivatives 6a and 6b. On the contrary, starting from alkyl beta -D-4-O-methanesulphonylpent-2-enoglyceropyranosides 21a-c, azides 22a-c were exclusively obtained. and subsequently converted into the corresponding amino derivatives 23a-c. The behaviour of P-anomers 21a-c was ascribed to steric interactions in the cyclic transition state, as supported by ab initio calculations. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(01)00450-5
• 作为产物：
  描述：

  乙酰化葡萄烯糖 在 咪唑 、 碘 、 potassium carbonate 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 1.0h， 生成 (2R,3S,6S)-2-((tert-butyldimethylsilyloxy)methyl)-6-methoxy-3,6-dihydro-2H-pyran-3-ol
  参考文献：
  名称：

  Linearization of carbohydrate derived polycyclic frameworks

  摘要：

  我们报告了一种易于获得的碳水化合物衍生的多样三环骨架，这对于探索多官能团手性脂环化合物可能有益。

  DOI：

  10.1039/c4ra04845h

文献信息

• Asymmetric Pauson−Khand Reaction. Cobalt-Mediated Cycloisomerization of 1,6-Enynes in Carbohydrate Templates:  Synthesis of Bis-Heteroannulated Pyranosides
  作者：José Marco-Contelles

  DOI：10.1021/jo961138w

  日期：1996.1.1

  The Pauson-Khand reaction on the carbohydrate derived precursors 1-6 is reported. We have described for the first time the cobalt-mediated cyclization of some O-branched chain 1,6-enynes in carbohydrate templates. The resulting bis-heteroannulated pyranosides 17-22 have been obtained in diastereomerically pure form, in moderate to good yield, and in one, simple synthetic operation. These enantiomerically

  据报道，在碳水化合物衍生的前体1-6上的Pauson-Khand反应。我们首次描述了碳水化合物模板中某些O支链1,6-烯炔的钴介导环化。以非对映体纯的形式，以中等至良好的收率，并且以一种简单的合成操作，获得了所得的双-异环吡喃糖苷17-22。这些对映体纯，稠密官能化的碳环是用于合成复杂天然产物的有吸引力的高级中间体。
• Osmium-Catalyzed Tethered Aminohydroxylation of Glycals: A Stereodirected Access to 2- and 3-Aminosugars
  作者：Stefania Mirabella、Francesca Cardona、Andrea Goti

  DOI：10.1021/ol503754f

  日期：2015.2.6

  The osmium-catalyzed aminohydroxylation of glycals has been achieved with complete regio- and stereocontrol by taking advantage of the Donohoe tethering approach. Glucals and galactals showed complementary reactivity in dependence of the stage at which the reaction was performed, i.e., directly or after double-bond shift consequent to a Ferrier rearrangement (that is, on the 1,2 or 2,3-unsaturated sugar), allowing access to both classes of 2-amino (mannosamine) and 3-amino (talosamine) sugar derivatives, respectively.