4,6-di-O-benzyl glucal | 203630-08-4

• 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-benzyl glucal
• 英文别名: 4,6-di-O-benzyl-D-glucal；(2R,3S,4R)-3-phenylmethoxy-2-(phenylmethoxymethyl)-3,4-dihydro-2H-pyran-4-ol
• CAS: 203630-08-4
• 化学式: C₂₀H₂₂O₄
• 分子量: 326.392
• InChiKey: ACSLJKNAGYSYRE-AQNXPRMDSA-N

物化性质

• 熔点：
  53 °C
• 沸点：
  476.7±45.0 °C(Predicted)
• 密度：
  1.19±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  24
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.3
• 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：

  4,6-di-O-benzyl glucal 在 indium(III) chloride 、 水 作用下， 以 乙腈 为溶剂， 反应 3.0h， 以77%的产率得到4,6-di-O-benzyl-2,3-dideoxy-D-erythro-hex-2-enopyranose
  参考文献：
  名称：

  InCl3–CH3CN–H2O: an efficient catalyst-solvent combination for the synthesis of Perlin aldehydes and related compounds. Application in the synthesis of unnatural l-azasugars

  摘要：

  InCl3-CH3CN-H2O has been found to be an efficient catalyst-solvent combination for the synthesis of Perlin aldehydes and related compounds. While acetylated glycals afforded the Perlin aldehydes directly with InCl3 and water, benzylated glycals on the other hand provided the hemiacetals under identical condition. The methodology reports a non-mercurial approach to Perlin aldehydes. Noteworthy is that this reaction is more facile as well as highly selective with glycals possessing a hydroxyl as a leaving group than with a benzyloxy group. Extension of this reaction to 2-C-hydroxymethyl glycals resulted in the formation of the corresponding hemiacetals, which were further transformed in to unsaturated azasugars with an exo-methylene group at C-2 position. Glycosidase inhibition studies reveal that these compounds display selectivity in inhibiting glucosidases rather than galactosidases. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2010.11.050
• 作为产物：
  描述：

  4,6-di-O-acetyl-D-glucal 在 咪唑 、 甲醇 、 四丁基氟化铵 、 sodium methylate 、 sodium hydride 、 溶剂黄146 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 mineral oil 为溶剂， 反应 2.42h， 生成 4,6-di-O-benzyl glucal
  参考文献：
  名称：

  基于 d-葡萄糖和 d-甘露糖的抗代谢物。第 4 部分：作为潜在有用的抗代谢物的 2-脱氧-d-葡萄糖前药的单乙酸酯和二乙酸酯的简便合成

  摘要：

  2-脱氧-d-葡萄糖 (2-DG) 是一种已知会干扰d-葡萄糖和d-甘露糖代谢的化合物，已被测试为潜在的抗癌和抗病毒剂。专注于 2-DG 的临床前和临床研究强调了与 2-DG 药物特性相关的一些局限性，例如较差的药代动力学特性。为了克服这个问题，我们提出了新型 2-DG前药的设计和合成，随后可以使用各种生化和分子方法进行测试。基于普遍存在的酯酶将再生 2-DG 的假设，我们在此将重点缩小到 2-DG 的酯作为潜在的前药，从而导致药物的循环时间增加以及充分的器官和肿瘤渗透。在体外，特别是在体内测试这一假设需要大量的纯单乙酰化和先前未知的 2-DG 水溶性衍生物。开发高效实用的合成方法势在必行。 我们描述了七种选择性乙酰化水溶性 2-DG 衍生物的新颖简便且可扩展的合成方法，并对所有最终产品进行了详细的1 H 和13 C NMR 分析。已对化合物 WP1122 进行了 X 射线衍射分析，该化合

  DOI：

  10.1016/j.carres.2023.108861

文献信息

• β-Type Glycosidic Bond Formation by Palladium-Catalyzed Decarboxylative Allylation
  作者：Shaohua Xiang、Zhiqiang Lu、Jingxi He、Kim Le MaiHoang、Jing Zeng、Xue-Wei Liu

  DOI：10.1002/chem.201303241

  日期：2013.10.11

  Decarboxylative allylation of glycals: A β‐type glycosidic bond has been constructed in high regio‐ and stereoselectivity by means of a palladium‐catalyzed decarboxylative O‐glycosylation. Various kinds of glycals with different protecting groups have been examined for this reaction to afford a diverse set of glycosylated products, including phenolic O‐glycosides, thiophenolic S‐glycoside, aliphatic

  糖类的脱羧烯丙基化：通过钯催化的脱羧O糖基化，以高区域和立体选择性构建了β型糖苷键。已对该反应进行了各种具有不同保护基的糖基的检测，以提供各种糖基化产物，包括酚O-糖苷，硫酚S-糖苷，脂族O-糖苷和具有出色的β-选择性和合理至优异的二糖。产量（请参阅计划）。
• Direct Ferrier rearrangement on unactivated glycals catalyzed by indium(III) chloride
  作者：Paramathevar Nagaraj、Namakkal G. Ramesh

  DOI：10.1016/j.tetlet.2009.04.084

  日期：2009.7

  Anhydrous InCl3 has been shown to efficiently catalyze the Ferrier rearrangement by a direct allylic substitution of the hydroxyl group at C-3 position of glycals to afford the corresponding 2,3-unsaturated glycosides in high yields at ambient temperature. This methodology obviates the need for protecting and/or activating the C-3 hydroxyl group of glycals. The reaction works in equal ease with both

  已经证明无水InCl 3通过在糖基的C -3位置上的羟基的直接烯丙基取代有效地催化费列重排，从而在环境温度下以高收率提供相应的2，3-不饱和糖苷。该方法避免了保护和/或活化糖基的C -3羟基的需要。将反应工作在同样容易与两个4,6-二ö苄基d -glucal和4,6-二- ö苄基d -galactal。InCl 3的温和性使该方法与具有酸不稳定基团的糖基受体兼容。反应的普遍性已通过多种醇，酚和糖亲核试剂得到证明。
• [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。
• <i>o</i> ‐Cyanobenzoate: A Recyclable and Reusable Stereo‐directing Group for β‐ <i>O</i> ‐Glycosylation via Pd(0)‐catalyzed Ferrier Rearrangement
  作者：Pradip Das、Mosidur Rahaman Molla、Amit Kumar、Rima Thakur

  DOI：10.1002/asia.202101156

  日期：2022.2

  Stereoselective synthesis of 2,3-dideoxy-β-O-glycosides has been reported herein. C3-(o-cyanobenzoate) ester protected glucal substrates have been efficiently glycosylated under Pd(0) catalyzed Ferrier rearrangement. The reaction was compatible with a large range of alcohol nucleophiles which afforded the rearranged products in high to excellent β-selectivities. Further, the successful recycling and reusing of the

  本文报道了2,3-二脱氧-β- O-糖苷的立体选择性合成。C3-( o-氰基苯甲酸酯) 酯保护的葡萄糖底物在Pd(0) 催化的Ferrier 重排下被有效地糖基化。该反应与大范围的醇亲核试剂相容，从而使重排产物具有高至优异的 β-选择性。此外，导向基团的成功回收和再利用使该方法有利于可持续化学。
• 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。