methyl 2-deoxy-β-D-arabino-hexopyranoside | 29084-15-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2-deoxy-β-D-arabino-hexopyranoside
• 英文别名: Methyl-2-desoxy-β-D-glucopyranosid；(2R,3S,4R,6R)-2-(hydroxymethyl)-6-methoxyoxane-3,4-diol
• CAS: 29084-15-9
• 化学式: C₇H₁₄O₅
• 分子量: 178.185
• InChiKey: UGCAWWFSBIEYGD-GBNDHIKLSA-N

物化性质

• 熔点：
  96-97 °C
• 沸点：
  349.3±42.0 °C(Predicted)
• 密度：
  1.33±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -1.1
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  79.2
• 氢给体数：
  3
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl 2-deoxy-β-D-arabino-hexopyranoside 在 palladium on activated charcoal 吡啶 、 N-溴代丁二酰亚胺(NBS) 、 sodium azide 、 氢气 、 silver fluoride 、 对甲苯磺酸 、 三乙胺 、 9-硼双环[3.3.1]壬烷 、 barium carbonate 作用下， 以 四氢呋喃 、 四氯化碳 、 乙醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， -15.0~60.0 ℃ 、2.67 kPa 条件下， 反应 37.0h， 生成 methyl 3-trifluoroacetamido-2,3-dideoxy-α-L-lyxo-hexopyranoside
  参考文献：
  名称：

  Synthesis of 6-Hydroxy-L-Daunosamine and L-Daunosamine Derivatives

  摘要：

  Methyl 3-trifluoroacetamido-2,3-dideoxy-alpha-L-lyxo-hexopyranoside (19) has been synthesized from D-glucose derivatives following two pathways. The first one involving 1,2:5,6-di-O-isopropylidene-alpha-D-glucopyranose as starting material is mainly based upon azidation at C-3, inversion of configuration at C-5 and then radical deoxygenation at C-2 (13 steps and 10% overall yield). This pathway also afforded methyl N-trifluoroacetyl-alpha-L-daunosamine 22. The second pathway, which started from tri-O-acetyl-D-glucal, relied essentially upon Michael addition of N3H on the corresponding hex-2-enose and glycosidation of the two pivaloyl compounds 33 and 34. After the beta-D-ribo isomer 34 was subsequently converted into its beta-methyl glycoside 28b, inversion of configuration at C-5 was carried out via the formation of the 6-bromo-sugar 36, followed by formation of the hex-5-enopyranoside 37. Hydroboration of 37 stereoselectively afforded 38, followed by catalytic hydrogenation and trifluoroacetylation to give 19.

  DOI：

  10.1080/07328309708006508
• 作为产物：
  描述：

  2-hydroxy-L-rhamnal acetate 在 四氯化碳 、 sodium amalgam 、 氨 、 水 、 溴 、 silver carbonate 作用下， 生成 methyl 2-deoxy-β-D-arabino-hexopyranoside
  参考文献：
  名称：

  Fischer,E.; Bergmann; Schotte, Chemische Berichte, 1920, vol. 53, p. 520

  摘要：

  DOI：

文献信息

• Selective C−O Bond Cleavage of Sugars with Hydrosilanes Catalyzed by Piers’ Borane Generated In Situ
  作者：Jianbo Zhang、Sehoon Park、Sukbok Chang

  DOI：10.1002/anie.201708109

  日期：2017.10.23

  [(C6F5)2BH], generated in situ, is demonstrated to promote the hydrosilylative reduction of sugars, providing a series of linear or cyclic polyols with high chemo- and regioselectivities under mild conditions. Studies of catalytic reactivity and regioselectivity with regard to the C−O bond cleavage with hydrosilanes suggest an importance of the steric environment around the anomeric carbon center of the

  Piers的硼烷[（C 6 F 5）2 BH]原位生成，可促进糖的氢化硅烷化还原，在温和条件下提供一系列具有高化学选择性和区域选择性的线性或环状多元醇。关于用氢硅烷裂解C-O键的催化反应性和区域选择性的研究表明，糖异头碳中心周围的空间环境很重要。
• Synthesis of MeON-neoglycosides of digoxigenin with 6-deoxy- and 2,6-dideoxy- d -glucose derivatives and their anticancer activity
  作者：Dong-dong Wang、Xiao-san Li、Yu-zhou Bao、Jie Liu、Xiao-kun Zhang、Xin-sheng Yao、Xue-Long Sun、Jin-Shan Tang

  DOI：10.1016/j.bmcl.2017.06.008

  日期：2017.8

  Cardiac glycosides show anticancer activities and their deoxy-sugar chains are vital for their anticancer effects. In order to study the structure-activity relationship (SAR) of cardiac glycosides toward cancers and get more potent anticancer agents, a series of MeON-neoglycosides of digoxigenin was synthesized and evaluated. First, ten 6-deoxy- and 2,6-dideoxy-d-glucopyranosyl donors were synthesized

  心脏苷具有抗癌活性，其脱氧糖链对其抗癌作用至关重要。为了研究强心苷与癌症的构效关系（SAR）并获得更有效的抗癌药，合成并评估了一系列洋地黄毒苷的MeON-新糖苷。首先，从甲基α - d-吡喃葡萄糖苷和2-deoxy- d开始合成十个6-deoxy-和2,6-dideoxy- d-吡喃葡萄糖基供体。-葡萄糖。同时，洋地黄毒苷是通过将市售的地高辛作为糖基受体进行酸性水解而获得的。然后，通过新糖基化方法成功地合成了地高辛配基的22人MeON-新糖苷文库。最后，评估了Nur77表达的诱导及其从细胞核到细胞质的转运以及这些MeON-新糖苷的细胞毒性。SAR分析表明，C3糖基化是诱导Nur77表达所必需的。此外，一些MeON-新糖苷（2b和8b）可显着诱导Nur77的表达及其从细胞核到细胞质的转运。然而，这些化合物对癌细胞的增殖没有抑制作用，表明它们可能不会诱导NIH-H460癌细胞的凋亡，其潜在的潜力和在癌细胞中的应用值得进一步研究。
• Efficient synthesis of α,β-unsaturated γ-lactones linked to sugars
  作者：Amélia P. Rauter、José Figueiredo、Maria Ismael、Tana Canda、Josep Font、Marta Figueredo

  DOI：10.1016/s0957-4166(01)00197-5

  日期：2001.5

  A series of structurally diverse unsaturated sugar-derived lactones has been prepared. α,β-Butenolides were introduced to the sugar moiety starting from epoxides, while α-methylene-γ-lactones were constructed from a carbonyl precursor, either an aldehyde, a ketone or a lactone. In the last case, an unprecedented Reformatsky-type reaction has been developed.

  已经制备了一系列结构多样的不饱和糖衍生的内酯。从环氧化物开始将α，β-丁烯内酯引入糖部分，而由羰基前体（醛，酮或内酯）构建α-亚甲基-γ-内酯。在最后一种情况下，开发了前所未有的Reformatsky型反应。
• Applications and Limitations of the I₂-Mediated Carbamate Annulation for the Synthesis of Piperidines: Five- versus Six-Membered Ring Formation
  作者：Hilary M. Corkran、Stefan Munneke、Emma M. Dangerfield、Bridget L. Stocker、Mattie S. M. Timmer

  DOI：10.1021/jo401512h

  日期：2013.10.4

  A protecting-group-free synthetic strategy for the synthesis of piperidines has been explored. Key in the synthesis is an I2-mediated carbamate annulation, which allows for the cyclization of hydroxy-substituted alkenylamines into piperidines, pyrrolidines, and furans. In this work, four chiral scaffolds were compared and contrasted, and it was observed that with both d-galactose and 2-deoxy-d-galactose

  已经探索了用于合成哌啶的无保护基的合成策略。在合成关键是I 2介导的氨基甲酸酯环，其允许羟基取代alkenylamines的环化成哌啶，吡咯烷，和呋喃。在这项工作中，4个手性支架，比较和对比，并且据观察，与两个d半乳糖和2-脱氧d半乳糖作为原料，将变换到是哌啶-1- deoxygalactonorjirimycin（DGJ）和4-外延-可以通过几个步骤和良好的总收率分别获得fagomine。当d葡萄糖被用作起始材料，只有呋喃产物形成，而使用2-脱氧的d-葡萄糖导致化学和立体选择性的降低以及四种产物的形成。可以提供每种环糊精产物形成的机理解释，这有助于我们更好地理解哌啶合成中氨基甲酸酯环糊精的范围和局限性。
• Syntheses of β-2-deoxy-D-glycosides assisted by glycosidases
  作者：Jean-Michel Petit、Françoise Paquet、Jean-Marie Beau

  DOI：10.1016/0040-4039(91)80769-3

  日期：1991.10

  Enzyme-catalyzed preparation of β-2-deoxy-D-glucosides and galactosides including disaccharides has been achieved using the corresponding glycals as substrates.

  使用相应的糖基作为底物，已经实现了酶催化的β-2-脱氧-D-葡萄糖苷和半乳糖苷（包括二糖）的制备。