3,4,6-三-O-乙酰基-alpha-D-吡喃葡萄糖1,2-(乙基原乙酸酯) | 3254-17-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 中文名称: 3,4,6-三-O-乙酰基-alpha-D-吡喃葡萄糖1,2-(乙基原乙酸酯)
• 英文名称: 3,4,6-tri-O-acetyl-1,2-O-(1-ethoxyethylidene)-α-D-glucopyranose
• 英文别名: 3,4,6-tri-O-acetyl-D-glucosyl-1,2-ortho-ester；3,4,6-Tri-O-acetyl-a-D-glucopyranose 1,2-(ethyl orthoacetate)；[(3aR,5R,6R,7S,7aR)-6,7-diacetyloxy-2-ethoxy-2-methyl-5,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-b]pyran-5-yl]methyl acetate
• CAS: 3254-17-9
• 化学式: C₁₆H₂₄O₁₀
• 分子量: 376.361
• InChiKey: ULBLUAFHNLHIND-VAZACWIESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  26
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  116
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  3,4,6-三-O-乙酰基-alpha-D-吡喃葡萄糖1,2-(乙基原乙酸酯) 在 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 0.75h， 生成 1,2-O-(1-ethoxyethylidene)-α-D-glucopyranose
  参考文献：
  名称：

  Epicoccamide D（一种天然存在的甘露糖基化的3-酰基四酸）的全合成和绝对构型

  摘要：

  作为天然糖四酸家族的第一个成员，用十八个步骤合成了真菌内代谢物表球菌酰胺D，产率为17％。合成的模块化特征也使人们可以使用具有不同糖和间隔基的类似物。它包含几个高收益的关键步骤。所述β- d -mannosyl组通过使用α-引入d -glucosyl亚氨酸酯与随后的氧化还原性差向异构化的供体在C-2'。吡咯烷环通过N-（β-酮酰基）-N-丙氨酸丙氨酸的Lacey-Dieckmann缩合定量关闭。将所得的3- [ω-（β- d -mannosyl）十八碳-2-烯酰基]特特拉姆酸是在铑催化剂的存在下（氢化ř，R）-[Rh（Et-DUPHOS）] [BF 4 ]建立（7 S）-立体中心。仅在将酰基四酸作为BF 2螯合物封端以防止金属催化剂被捕获后才有可能。我们还分配了天然产品的迄今未知的结构为5小号，7小号通过其的比较13 C NMR光谱和光学旋转数据与我们的两种合成5的小号，7 - [R / š

  DOI：

  10.1002/chem.201301914
• 作为产物：
  描述：

  β-D-葡萄糖五乙酸酯 在 三乙基硅烷 、 lutidine 、 四丁基溴化铵 、 碘 作用下， 以 二氯甲烷 为溶剂， 生成 3,4,6-三-O-乙酰基-alpha-D-吡喃葡萄糖1,2-(乙基原乙酸酯)
  参考文献：
  名称：

  Efficient and direct synthesis of saccharidic 1,2-ethylidenes, orthoesters, and glycals from peracetylated sugars via the in situ generation of glycosyl iodides with I2/Et3SiH

  摘要：

  Peracetylated sugars can be efficiently converted into the corresponding 1,2-ethylidenes, -orthoesters, and -glycals via the in situ generation of glycosyl iodides promoted by I-2/Et3SiH. The approach is straightforward and avoids isolation of the sensitive iodinated intermediates. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2003.09.022

文献信息

• Total Synthesis of Myrmekioside A, a Mono-<i>O</i>-alkyl-diglycosylglycerol from Marine Sponge<i>Myrmekioderma</i>sp.
  作者：Jun Zhang、Chunxia Li、Linlin Sun、Guangli Yu、Huashi Guan

  DOI：10.1002/ejoc.201500471

  日期：2015.7

  Myrmekioside A, which was isolated from the marine sponge Myrmekioderma sp. as a member of the family of natural mono-O-alkyl-diglycosylglycerols, and which has a strong reversion effect on the tumor cell morphology of ras-transformed cells at 5 μg/mL, was synthesized for the first time in 17 steps and 14 % overall yield. The β-glycosidic linkages in myrmekioside A were successfully constructed by

  Myrmekioside A，它是从海洋海绵 Myrmekioderma sp. 中分离出来的。作为天然单-O-烷基-二糖基甘油家族的一员，5 μg/mL对ras转化细胞的肿瘤细胞形态有很强的逆转作用，首次分17步和14步合成% 总产率。myrmekioside A 中的 β-糖苷键是通过使用三氯乙酰亚胺和硫代糖苷作为糖基供体的相邻基团参与方法成功构建的。甘油主链 C-2 处的 2R 绝对构型源自 (S)-1,2- 异丙基甘油 (8)。这种合成方法可能适用于制备其他具有不同糖和烷基链的桃金娘苷类似物，用于进一步的结构-活性关系研究。
• A practical synthesis of β-d-mannopyranosides
  作者：Alois Fürstner、Ingo Konetzki

  DOI：10.1016/s0040-4039(98)01163-0

  日期：1998.8

  An indirect yet highly efficient protocol for the β-d-mannosylation of sterically hindered alcohols is reported. Trichloroacetimidate 5 is used a key building block which is converted into the desired mannosides 9 via triflates 8 by an ultrasound promoted β-d-gluco → β-d-manno inversion process.

  据报道，用于空间受阻醇的β- d-甘露糖基化的间接但高效的方案。三氯乙酰亚胺酯5被使用的密钥构建块被转换成期望的甘露糖苷9通过三氟甲磺酸酯8通过超声波促进β- d -葡糖→β- d -甘露反转处理。
• Stereoselective Ring-Opening of Acetylated Pyranose-1,2-(etyl orthoacetates).
  作者：Setsuo SAITO、Shigeya SUMITA、Koki ICHINOSE、Yasuhiko KANDA

  DOI：10.1248/cpb.41.90

  日期：——

  When acetylated pyranose-1, 2-(ethyl orthyl orthoacetates) were hydrolyzed in acidic solvents, the ring-opening of the orthoacetate rings was influenced by the axial or equatorial OAc group at C-4 on the pyranoses; on acid-catalyzed hydrolysis, 3, 4, 6-tri-O-acetyl-α-D-glactopyranose- (8) and methyl 3, 4-di-O-acetyl-α-D-galacturonatopyranose-1, 2-(ethyl orthoacetate) (16) having an axial OAc group at C-4 on the pyranose rings gave 1, 3, 4, 6-tetra-O-acetyl-α-D-galactopyranose (9) and methyl 1, 3, 4-tri-O-acetyl-α-D-galacturonatopyranose (23), respectively, whereas 3, 4, 6-tri-O-acetyl-α-D-glucopyranose- (10) and methyl 3, 4-di-O-acetyl-α-D-glucuronatopyranose-1, 2-(ethyl orthoacetate) (22)having an equatorial OAc group at C-4 on the pyranose rings gave 2, 3, 4, 6-tetra-O-acetyl-D-glucopyranose (11) and methyl 2, 3, 4-tri-O-acetyl-D-glucuronatopyranose (24), respectively. On the acid-catalyzed hydrolysis, 3, 4-di-O-acetyl-β-L-arabinopyranose-1, 2-(ethyl orthoacetate) (34) having an axial OAc group at C-4 on the pyranose ring gave a mixture of 1, 3, 4-tri-O-acetyl-β-L- (35) and 2, 3, 4-tri-O-acetyl-L-arabinopyranose (36). These selectivities of ring-opening of the 1, 2-(orthoacetates) were considered to have resulted from the differences of the conformers fo the 1, 2-(orthoacids)intermediates derived from the 1, 2-(othoacetates) and the orientation of the acetyl groups at C-4 on the pyranose rings.

  当乙酰化的吡喃糖1,2-(乙基邻酸酯)在酸性溶剂中水解时，邻酸酯环的开环受吡喃糖C-4位点的轴向或赤道OAc基团的影响；在酸催化水解过程中，具有C-4轴向OAc基团的3,4,6-三-O-乙酰-α-D-半乳糖吡喃糖-(8)和甲基3,4-二-O-乙酰-α-D-半乳糖酸吡喃糖-1,2-(乙基邻酸酯)(16)分别生成1,3,4,6-四-O-乙酰-α-D-半乳糖吡喃糖(9)和甲基1,3,4-三-O-乙酰-α-D-半乳糖酸吡喃糖(23)，而具有C-4赤道OAc基团的3,4,6-三-O-乙酰-α-D-葡萄糖吡喃糖-(10)和甲基3,4-二-O-乙酰-α-D-葡萄糖醛酸吡喃糖-1,2-(乙基邻酸酯)(22)则分别生成2,3,4,6-四-O-乙酰-D-葡萄糖吡喃糖(11)和甲基2,3,4-三-O-乙酰-D-葡萄糖醛酸吡喃糖(24)。在酸催化水解过程中，具有C-4轴向OAc基团的3,4-二-O-乙酰-β-L-阿拉伯糖吡喃糖-1,2-(乙基邻酸酯)(34)生成1,3,4-三-O-乙酰-β-L-(35)和2,3,4-三-O-乙酰-L-阿拉伯糖吡喃糖(36)的混合物。这些1,2-(邻酸酯)的开环选择性被认为是由1,2-(邻酸)中间体的构象差异以及吡喃糖环上C-4位置的乙酰基团的取向所导致的。
• Molecular sieves 5A as an acidic reagent: the discovery and applications
  作者：Noriaki Asakura、Tsukasa Hirokane、Hayato Hoshida、Hidetoshi Yamada

  DOI：10.1016/j.tetlet.2010.11.113

  日期：2011.1

  The first use of molecular sieves (MS) 5A as an acidic reagent is described. We observed the acidic property during a dehydration reaction of 2-methyl-4-phenyl-3-butyn-2-ol. The acidity was sufficient to introduce ethoxyethyl and methoxyisopropyl protecting groups into alcohols. Additionally, the employment of MS 5A improved the synthesis of 1,2,4-orthoacetyl-α-d-glucopyranose at the intramolecular

  描述了分子筛（MS）5A作为酸性试剂的首次使用。我们观察到了2-甲基-4-苯基-3-丁炔-2-醇的脱水反应过程中的酸性。酸度足以将乙氧基乙基和甲氧基异丙基保护基引入醇中。另外，MS 5A的使用改善了分子内原酸酯交换步骤中1,2,4-原乙酰基-α - d-吡喃葡萄糖的合成。在合成的另一步骤中，还应用了MS 4A来证明MS的操作简化了总体操作。
• 3, 6-O-BRIDGED PYRANOSE INVERSION COMPOUND AND PROCESS FOR PRODUCING B-O-PYRANOSIDE
  申请人：Yamada Hidetoshi

  公开号：US20100324275A1

  公开（公告）日：2010-12-23

  An object of the present invention is to provide a 3,6-O-bridged pyranose-inverted compound useful for being easy to produce β-O-pyranosides selectively. The 3,6-O-bridged pyranose-inverted compound according to the present invention is represented by General Formula (1): wherein R A and R B each represent hydrogen or are bonded to each other to form a benzene ring; one of R C and R D represents hydrogen and the other represents —OR 2 ; R 1 represents hydroxy or halogen; and R 2 and R 3 each represent a hydroxy-protecting group.

  本发明的一个目的是提供一种3,6-O-桥联吡喃糖倒置化合物，用于易于选择性地生产β-O-吡喃糖苷。根据本发明，3,6-O-桥联吡喃糖倒置化合物由通式（1）表示：其中RA和RB分别表示氢原子或结合在一起形成苯环；RC和RD中的一个表示氢原子，另一个表示—OR2；R1表示羟基或卤素；R2和R3各自表示一个羟基保护基团。