tetra-O-benzoyl-2-deoxy-α-D-arabino-hexopyranose | 51842-43-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: tetra-O-benzoyl-2-deoxy-α-D-arabino-hexopyranose
• 英文别名: 2-deoxy-1,3,4,6-tetra-O-benzoyl-α-D-glucopyranose；[(2R,3S,4R,6R)-3,4,6-tribenzoyloxyoxan-2-yl]methyl benzoate
• CAS: 51842-43-4
• 化学式: C₃₄H₂₈O₉
• 分子量: 580.591
• InChiKey: IZDUSRZYYKMIMV-CSBHBGLHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  43
• 可旋转键数：
  13
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  114
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为产物：
  描述：

  2,3,4,6-tetra-O-benzoylglucosyl bromide 在 四(三苯基膦)钯 、 N,N-二异丙基乙胺 作用下， 以 醋酸异丙酯 为溶剂， 反应 20.0h， 以95%的产率得到tetra-O-benzoyl-2-deoxy-α-D-arabino-hexopyranose
  参考文献：
  名称：

  激发态钯催化 1,2-自旋中心转移可实现碳水化合物的选择性 C-2 还原、氘化和碘化

  摘要：

  激发态催化是一种涉及一种或多种激发态催化物质的过程，已成为有机合成中的强大工具，因为它允许进入激发态反应景观以发现新颖的化学反应性。在此，我们报告了第一个激发态钯催化的 1,2-自旋中心转移反应，该反应能够实现碳水化合物的位点选择性功能化。该策略的特点是反应条件温和，具有高水平的区域和立体选择性，可耐受多种官能团和复杂的分子结构。机理研究表明，一种根本机制涉及杂合钯物种的形成，该杂合钯物种经历1,2-自旋中心转移，然后进行还原、氘化和碘化，以提供功能化的2-脱氧糖。新的反应性将为快速生成天然和非天然碳水化合物提供通用方法。

  DOI：

  10.1021/jacs.0c11209

文献信息

• Practical synthesis of 2-deoxy sugars <i>via</i> metal free deiodination reactions
  作者：Wang Yao、Hao Wang、Jing Zeng、Qian Wan

  DOI：10.1080/07328303.2021.2015365

  日期：2021.11.22

  Abstract 2-Deoxy-glycosides, in which the C-2 hydroxyl group is replaced with a hydrogen atom, are important motifs in numerous bioactive natural products and pharmaceutical molecules. Herein, an improved dilauroyl peroxide-mediated radical deiodination reaction by using cyclohexane and ethyl acetate as co-solvent is reported. This is an environmentally benign protocol, which operates smoothly under

  摘要 2-脱氧糖苷，其中 C-2 羟基被氢原子取代，是许多生物活性天然产物和药物分子中的重要基序。本文报道了一种使用环己烷和乙酸乙酯作为共溶剂的改进的过氧化二月桂酰介导的自由基脱碘反应。这是一种对环境无害的方案，可在温和条件下平稳运行，并允许以高达 98% 的收率有效制备一系列 2-脱氧糖苷。
• Deoxygenation of carbohydrates by thiol-catalysed radical-chain redox rearrangement of the derived benzylidene acetals
  作者：Hai-Shan Dang、Brian P. Roberts、Jasmeet Sekhon、Teika M. Smits

  DOI：10.1039/b212303g

  日期：2003.4.14

  efficient thiol-catalysed radical-chain redox rearrangement resulting in deoxygenation at one of the diol termini and formation of a benzoate ester function at the other. The role of the thiol is to act as a protic polarity-reversal catalyst to promote the overall abstraction of the acetal hydrogen atom by a nucleophilic alkyl radical. The redox rearrangement is carried out in refluxing octane and/or chlorobenzene

  衍生自碳水化合物中1,2-或1,3-二醇官能团的五元或六元环状亚苄基乙缩醛经过有效的硫醇催化的自由基链氧化还原重排，导致一个二醇末端的脱氧并形成一个苯甲酸酯的作用相反。硫醇的作用是充当质子极性反转催化剂，以促进亲核烷基自由基对乙缩醛氢原子的整体提取。氧化还原重排是在回流辛烷和/或氯苯作为溶剂的条件下进行的。温度为130摄氏度，由热分解二叔丁基过氧化物（DTBP）或2,2-双（叔丁基过氧）丁烷引发。硅烷硫醇（Bu（t）O）3SiSH和Pr（i）3SiSH（TIPST）是特别有效的催化剂，DTBP与TIPST结合使用通常是最有效和方便的组合。该反应已通过1，2-，3，4-和4，6-O-亚苄基吡喃糖酶和5，6-O-亚苄基呋喃糖用于各种单糖的单脱氧。它也已被用于引起甘露糖和二糖α，α-海藻糖的双脱氧。对甲氧基亚苄基乙缩醛的使用没有太大优势，并且在相似条件下，乙缩醛不会发生明显的氧化还原重排。官能团
• Giese, Bernd; Gilges, Stefan; Groeninger, Kay S., Liebigs Annalen der Chemie, 1988, p. 615 - 617
  作者：Giese, Bernd、Gilges, Stefan、Groeninger, Kay S.、Lamberth, Clemens、Witzel, Tom

  DOI：——

  日期：——
• NaBH3CN and other systems as substitutes of tin and silicon hydrides in the light or heat-initiated reduction of halosugars: a tunable access to either 2-deoxy sugars or 1,5-anhydro-itols
  作者：Isabelle Bruyère、Zoltan Tóth、Hamida Benyahia、Jia Lu Xue、Jean-Pierre Praly

  DOI：10.1016/j.tet.2013.09.032

  日期：2013.11

  UV light-promoted reduction of acetobromoglucose by NaBH3CN in t-BuOH afforded 1,3,4,6-tetra-O-acetyl-2-deoxy-alpha-D-arabino-hexopyranose in high yield and purity, via a Surzur-Tanner rearrangement, while, with 10 mol % thiophenol added, acetylated 1,5-anhydro-D-glucitol was cleanly obtained. Such tin-free and mild reductions, presumed to proceed via radical pathways, were more efficient with NaBH3CN compared to NaBH4 or NaBD4, and do not occur with acetochloroglucose. Similar reductions to 1,3,4,6-tetra-O-acetyl-2-deoxy-alpha-D-arabino-hexopyranose were achieved upon heating to 80 degrees C t-BuOH or CH3CN solutions of NaBH3CN and AIBN, but with a lower selectivity due to competing ionic reactions. With other pyranosyl bromides, reductions by NaBH3CN could be tuned similarly (D-galacto), but some (D-manno, 5-thio-D-xylo) gave mainly or exclusively 1,5-anhydro-itols. Other conditions, or reagents promoting SET process, afforded also reduced products, but with lower rates or selectivities. Primary iodides were reduced readily with NaBH3CN under UV light. (c) 2013 Elsevier Ltd. All rights reserved.
• Synthesis of 2-deoxy-1-and -6-thio-d-arabino-hexose and several S-dialkylarsino derivatives
  作者：Maria V. Rosenthal、Ralph A. Zingaro

  DOI：10.1016/s0008-6215(00)85564-0

  日期：1980.9