4-O-benzyl-6-O-tert-butyldimethylsilyl-D-(-)-glucal | 137792-62-2

• 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: 4-O-benzyl-6-O-tert-butyldimethylsilyl-D-(-)-glucal
• 英文别名: (2R,3S,4R)-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-3-phenylmethoxy-3,4-dihydro-2H-pyran-4-ol
• CAS: 137792-62-2
• 化学式: C₁₉H₃₀O₄Si
• 分子量: 350.53
• InChiKey: CRTVTNZFAFIEQK-KURKYZTESA-N

物化性质

• 熔点：
  55-57 °C
• 沸点：
  422.9±45.0 °C(Predicted)
• 密度：
  1.05±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.87
• 重原子数：
  24
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  47.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4-O-benzyl-6-O-tert-butyldimethylsilyl-D-(-)-glucal 在 咪唑 、 4 A molecular sieve 、 四丁基氟化铵 、 N,N-二异丙基乙胺 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 12.0h， 生成 4-O-Benzyl-6-O-(tert-butyldimethylsilyl)-1,2,7,8-tetradeoxy-3-O-(methoxymethyl)-L-galacto-D-altro-octa-1,7-dieno-1,5-pyranose
  参考文献：
  名称：

  Radical cyclization routes to bridged pyranosides as precursors of densely functionalized cycloalkanes

  摘要：

  Glycals derived from hexopyranoses permit the incorporation of iodine at C-2 as well as elaboration of an olefinic residue via the C-5-hydroxymethyl group. Radical cyclization of these functionalities leads to bicyclic systems whose bridge sizes depend on the lengths of the olefinic appendages. Hydrolysis of the anomeric centers of the [2.2.1] structures leads spontaneously to cyclopentane derivatives. However, with [2.2.2] structures, the hemiacetal intermediates are stable in bicyclic forms but are opened readily upon mcerpatolysis with propane dithiol to give cyclohexane derivatives.

  DOI：

  10.1021/jo00028a033
• 作为产物：
  描述：

  叔丁基二甲基氯硅烷 在 吡啶 、 咪唑 、 四丁基碘化铵 、 potassium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 7.58h， 生成 4-O-benzyl-6-O-tert-butyldimethylsilyl-D-(-)-glucal
  参考文献：
  名称：

  Radical cyclization routes to bridged pyranosides as precursors of densely functionalized cycloalkanes

  摘要：

  Glycals derived from hexopyranoses permit the incorporation of iodine at C-2 as well as elaboration of an olefinic residue via the C-5-hydroxymethyl group. Radical cyclization of these functionalities leads to bicyclic systems whose bridge sizes depend on the lengths of the olefinic appendages. Hydrolysis of the anomeric centers of the [2.2.1] structures leads spontaneously to cyclopentane derivatives. However, with [2.2.2] structures, the hemiacetal intermediates are stable in bicyclic forms but are opened readily upon mcerpatolysis with propane dithiol to give cyclohexane derivatives.

  DOI：

  10.1021/jo00028a033

文献信息

• [EN] MOLECULAR PROBES FOR ANALYSIS OF METABOLISM OF GLYCOLYSIS INHIBITORS PRODRUGS AND SYNTHESIS METHODS THEREFORE<br/>[FR] SONDES MOLÉCULAIRES POUR L'ANALYSE DU MÉTABOLISME D'INHIBITEURS DE GLYCOLYSE ET LEURS PROCÉDÉS DE SYNTHÈSE
  申请人：DERMIN SP Z O O

  公开号：WO2020035782A1

  公开（公告）日：2020-02-20

  The present invention relates to compounds according to structure (I) whereby one of R1 to R3 is -OCOCD3 and the other two are either hydroxyl or OAc, their synthesis and their use in for the analysis of the metabolism of glycolysis inhibitors.

  本发明涉及具有结构(I)的化合物，其中R1至R3中的一个为-OCOCD3，其余两个为羟基或OAc，以及它们的合成及其在分析糖酵解抑制剂代谢中的应用。
• σ-Ferrier rearrangement of carbohydrate derived vinylcyclopropanes: a facile approach to oxepane analogs
  作者：Venkataraman Ganesh、Taraknath Kundu、Srinivasan Chandrasekaran

  DOI：10.1016/j.tet.2014.07.004

  日期：2014.10

  carbohydrate derived vinylcyclopropanes (VCPs) under electrophilic conditions mediated by chloramine-T and a phase-transfer catalyst. The present work serves as the first example on the studies of the reactivity of carbohydrate VCPs towards the synthesis of densely functionalized oxepane analogues. The work elaborates on a reasonable mechanism for the product formation and our observations on the diastereoselectivity

  本文介绍了我们在由氯胺-T和相转移催化剂介导的亲电条件下，对碳水化合物衍生的乙烯基环丙烷（VCP）进行σ-Ferrier环扩展的工作。本工作作为研究碳水化合物VCPs对高密度官能化的环氧庚烷类似物合成反应性的第一个例子。这项工作详细阐述了产物形成的合理机理，以及我们根据控制实验和气相计算得出的非对映选择性的观察结果。
• A New Procedure for the Preparation of β-Keto-δ-lactones from Sugars and Their Transformation into Glycosyl Acceptors in Disaccharides Synthesis
  作者：Alessandra Bartolozzi、Giuseppe Capozzi、Stefano Menichetti、Cristina Nativi

  DOI：10.1021/ol991176c

  日期：2000.2.1

  materials for the synthesis of enantiopure beta-ketone-delta-lactones. They are easily transformed, through a two-step, one-pot reaction, into the corresponding alpha,alpha'-dioxothiones which in turn can be quantitatively trapped with dienophiles in inverse electron-demand [4 + 2] cycloadditions. The reaction of dioxothione 8b with endo and exo glucals allowed the elaboration of a new protocol to prepare

  [反应：见正文]乙二醇是合成对映纯β-酮-δ-内酯的有效起始原料。通过两步一锅反应，它们很容易转化为相应的α，α'-二氧噻吩硫酮，而后者又可以被反电子需求的[4 + 2]环加成中的亲二烯体定量捕集。二氧噻硫酮8b与内和外葡糖的反应允许拟订新的方案以立体选择性地制备2-硫代-或2-脱氧二糖。
• Catalytic Olefin Hydroamidation Enabled by Proton-Coupled Electron Transfer
  作者：David C. Miller、Gilbert J. Choi、Hudson S. Orbe、Robert R. Knowles

  DOI：10.1021/jacs.5b09671

  日期：2015.10.28

  Here we report a ternary catalyst system for the intramolecular hydroamidation of unactivated olefins using simple N-aryl amide derivatives. Amide activation in these reactions occurs via concerted proton-coupled electron transfer (PCET) mediated by an excited state iridium complex and weak phosphate base to furnish a reactive amidyl radical that readily adds to pendant alkenes. A series of H-atom, electron, and proton transfer events with a thiophenol cocatalyst furnish the product and regenerate the active forms of the photocatalyst and base. Mechanistic studies indicate that the amide substrate can be selectively homolyzed via PCET in the presence of the thiophenol, despite a large difference in bond dissociation free energies between these functional groups.
• [EN] ESTERS OF 2-DEOXY-MONOSACCHARIDES WITH ANTI PROLIFERATIVE ACTIVITY<br/>[FR] ESTERS DE 2-DÉSOXY-MONOSACCHARIDES AYANT UNE ACTIVITÉ ANTIPROLIFÉRATIVE
  申请人：UNIV TEXAS

  公开号：WO2014165736A3

  公开（公告）日：2014-11-27