4,6-di-O-benzoyl-1,5-anhydro-2-deoxy-D-erythro-hex-1-en-3-ulose | 1075748-99-0

• 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: 4,6-di-O-benzoyl-1,5-anhydro-2-deoxy-D-erythro-hex-1-en-3-ulose
• 英文别名: [(2R,3R)-3-benzoyloxy-4-oxo-2,3-dihydropyran-2-yl]methyl benzoate
• CAS: 1075748-99-0
• 化学式: C₂₀H₁₆O₆
• 分子量: 352.343
• InChiKey: PCECTVXBFXHRCR-MSOLQXFVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  26
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.15
• 拓扑面积：
  78.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  4,6-di-O-benzoyl-1,5-anhydro-2-deoxy-D-erythro-hex-1-en-3-ulose 在 1,10-菲罗啉 、 palladium 10% on activated carbon 、 氢气 、 氧气 、 palladium diacetate 作用下， 以 乙酸乙酯 、 N,N-二甲基甲酰胺 为溶剂， 反应 4.0h， 生成 ((2R,3S,4R,6R)-3-(benzoyloxy)-4-hydroxy-6-phenyltetrahydro-2H-pyran-2-yl)methyl benzoate
  参考文献：
  名称：

  通过C-1芳基烯酮立体选择性制备β-芳基-C-糖苷的途径的开发。

  摘要：

  宽范围的烯酮衍生自d -glucal，d -galactal，升-rhamnal，d -rhamnal，和升-arabinal后行与各种芳基硼酸轴承供电子和在乙酸钯的存在吸电子基团的Heck耦合和1,10-菲咯啉。这些反应以良好的产率提供了合成上有用的C -1芳基烯酮。在优化的条件下，芳基硼酸和烯酮中分别存在的许多敏感官能团和保护基团保持完整。C -1芳基烯酮与Pd-C / H 2的立体选择性加氢提供2-脱氧芳基-C的β-异构体-糖苷具有优异的产率。所述C- 1芳基烯酮也被用来作为用于2-羟基β -芳基-的合成前体Ç -glycosides。以优异的产率实现了C -1芳基烯酮的区域选择性C -2卤化和乙烯基化。

  DOI：

  10.1021/acs.orglett.0c02843
• 作为产物：
  描述：

  乙酰化葡萄烯糖 在 吡啶 、 甲醇 、 重铬酸吡啶 、 potassium carbonate 作用下， 反应 36.0h， 生成 4,6-di-O-benzoyl-1,5-anhydro-2-deoxy-D-erythro-hex-1-en-3-ulose
  参考文献：
  名称：

  通过C-1芳基烯酮立体选择性制备β-芳基-C-糖苷的途径的开发。

  摘要：

  宽范围的烯酮衍生自d -glucal，d -galactal，升-rhamnal，d -rhamnal，和升-arabinal后行与各种芳基硼酸轴承供电子和在乙酸钯的存在吸电子基团的Heck耦合和1,10-菲咯啉。这些反应以良好的产率提供了合成上有用的C -1芳基烯酮。在优化的条件下，芳基硼酸和烯酮中分别存在的许多敏感官能团和保护基团保持完整。C -1芳基烯酮与Pd-C / H 2的立体选择性加氢提供2-脱氧芳基-C的β-异构体-糖苷具有优异的产率。所述C- 1芳基烯酮也被用来作为用于2-羟基β -芳基-的合成前体Ç -glycosides。以优异的产率实现了C -1芳基烯酮的区域选择性C -2卤化和乙烯基化。

  DOI：

  10.1021/acs.orglett.0c02843

文献信息

• Efficient Synthesis of Rare Sugar <scp>d</scp>-Allal via Reversal of Diastereoselection in the Reduction of Protected 1,5-Anhydrohex-1-en-3-uloses: Protecting Group Dependence of the Stereoselection
  作者：Takashi Fujiwara、Masahiko Hayashi

  DOI：10.1021/jo801596q

  日期：2008.11.21

  loses using the NaBH4CeCl3 x 7 H2O system. The crucial point of this synthesis is the nature of the protecting group. When bulky silyl group such as t-butyldiphenylsilyl was used as substrate, protected D-allal was obtained in >99% selectivity. In contrast, when acetylated enone was used, protected D-glucal was obtained exclusively. The addition of CeCl3 x 7 H2O was also found to influence selectivity

  D-alal是通过使用NaBH4CeCl3 x 7 H2O系统还原大体积的甲硅烷基保护的1，5-脱水己基-1-en-3-uloses选择性获得的。该合成的关键点是保护基团的性质。当使用大体积的甲硅烷基如叔丁基二苯基甲硅烷基作为底物时，以> 99％的选择性获得了受保护的D-alal。相反，当使用乙酰化的烯酮时，仅获得保护的D-葡萄糖。还发现添加CeCl3 x 7 H2O会影响选择性。
• Palladium‐Catalyzed Reaction of Aryl Iodides and Glycal Enones: Application in the Preparation of Dapagliflozin Analogues
  作者：Adesh Kumar Singh、Rapelly Venkatesh、Vimlesh Kumar Kanaujiya、Varsha Tiwari、Jeyakumar Kandasamy

  DOI：10.1002/ejoc.202200023

  日期：2022.9.6

  A wide range of aryl iodides bearing electron-donating and withdrawing groups underwent oxidative C-1 arylation with enones derived from glycals in the presence of Pd(OAc)2 and AgNO3 under ligand-free conditions. The developed methodology was successfully applied in the preparation of dapagliflozin analogues (SGLT-2 inhibitor).

  在无配体条件下，在 Pd(OAc) 2和 AgNO 3存在下，各种带有给电子基团和吸电子基团的芳基碘化物与衍生自糖醛的烯酮发生氧化C -1 芳基化。所开发的方法成功地应用于制备达格列净类似物（SGLT-2 抑制剂）。
• Palladium-Catalyzed Stereocontrolled Synthesis of Aryl-C-Glycosides from Arylboronic Acids and Glycal Enones Through 1,4-Conjugate Addition Reactions
  作者：Jeyakumar Kandasamy、Adesh Kumar Singh、Rapelly Venkatesh

  DOI：10.1055/a-2179-8669

  日期：2024.4

  4-Conjugate addition of arylboronic acids to the glycal enones delivered 2-deoxy-α-aryl-C-glycosides in good yields. The reaction was catalyzed by palladium acetate in the presence of trifluoroacetic acid and 1,10-phenanthroline. A wide range of glycal enones derived from d-glucal, d-galactal, and d-rhamnal participated in the coupling reaction with different arylboronic acids smoothly. Different protecting

  芳基硼酸与糖醛酸的 1,4-共轭加成反应以良好的产率生成 2-脱氧-α-芳基-C-糖苷。该反应在三氟乙酸和1,10-菲咯啉存在下由乙酸钯催化。来自d-葡萄糖、d-半乳糖和d-鼠李醛的多种糖醛烯酮顺利地参与了与不同芳基硼酸的偶联反应。包括苄基、乙酰基、新戊酰基和苯甲酰基在内的不同保护基团在优化条件下是相容的。
• Microwave-assisted stereoselective α-2-deoxyglycosylation of hex-1-en-3-uloses
  作者：Hui-Chang Lin、Hsu-Hsuan Wu、Zi-Ping Lin、Chih-Yuan Lin、Chun-Hung Lin、Kun-Lung Chen、Fung Fuh Wong

  DOI：10.1016/j.tetlet.2009.10.049

  日期：2009.12

  alpha-2-Deoxyglycosides were successfully synthesized by means of microwave-assisted glycosylation. Hex-1-en-3-uloses were treated with a catalytic amount of AlCl3 and various O-nucleophiles including alcohols and sugars under microwave conditions. The desired alpha-2-deoxy-ulosides products were obtained in good to excellent yields with high stereoselectivity (alpha/beta >= 88/12). Crown Copyright (C) 2009 Published by Elsevier Ltd. All rights reserved.
• Development of Routes for the Stereoselective Preparation of β-Aryl-<i>C</i>-glycosides via <i>C</i>-1 Aryl Enones
  作者：Adesh Kumar Singh、Vimlesh Kumar Kanaujiya、Varsha Tiwari、Shahulhameed Sabiah、Jeyakumar Kandasamy

  DOI：10.1021/acs.orglett.0c02843

  日期：2020.10.2

  various arylboronic acids bearing electron-donating and -withdrawing groups in the presence of palladium acetate and 1,10-phenanthroline. These reactions provided synthetically useful C-1 aryl enones in good yields. Many sensitive functional groups as well as protecting groups present in arylboronic acids and enones, respectively, remained intact under optimized conditions. The stereoselective hydrogenation

  宽范围的烯酮衍生自d -glucal，d -galactal，升-rhamnal，d -rhamnal，和升-arabinal后行与各种芳基硼酸轴承供电子和在乙酸钯的存在吸电子基团的Heck耦合和1,10-菲咯啉。这些反应以良好的产率提供了合成上有用的C -1芳基烯酮。在优化的条件下，芳基硼酸和烯酮中分别存在的许多敏感官能团和保护基团保持完整。C -1芳基烯酮与Pd-C / H 2的立体选择性加氢提供2-脱氧芳基-C的β-异构体-糖苷具有优异的产率。所述C- 1芳基烯酮也被用来作为用于2-羟基β -芳基-的合成前体Ç -glycosides。以优异的产率实现了C -1芳基烯酮的区域选择性C -2卤化和乙烯基化。