1,5-anhydro-2-deoxy-2-formyl-3,4,6-tri-O-methyl-D-arabino-hex-1-enitol | 136883-90-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 乙烯酯类
• 英文名称: 1,5-anhydro-2-deoxy-2-formyl-3,4,6-tri-O-methyl-D-arabino-hex-1-enitol
• 英文别名: 1,5-Anhydro-2-deoxy-C-2-formyl-3,4,6-tri-O-methyl-D-arabino-hex-1-enitol；3,4,6-tri-O-methyl-D-glucal；3,4,6-tri-O-methyl-2-C-formyl-D-glucal；2-formyl-3,4,6-tri-O-methyl-D-glucal；3,4,6-tri-O-methyl-glucal-2-carboxaldehyd；(2R,3S,4R)-3,4-dimethoxy-2-(methoxymethyl)-3,4-dihydro-2H-pyran-5-carbaldehyde
• CAS: 136883-90-4
• 化学式: C₁₀H₁₆O₅
• 分子量: 216.234
• InChiKey: LJIFFJAXIUVGHV-OPRDCNLKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.8
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1,5-anhydro-2-deoxy-2-formyl-3,4,6-tri-O-methyl-D-arabino-hex-1-enitol 在 sodium tetrahydroborate 、 三氟化硼乙醚 、 间氯过氧苯甲酸 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 1.42h， 生成 (4R,5S,6R)-4,5-Dimethoxy-6-methoxymethyl-3-methylene-tetrahydro-pyran-2-one
  参考文献：
  名称：

  Synthesis of C-2 Methylene O- and C-Glycosides and Sugar Derived α-Methylene-δ-valerolactones from C-2-Acetoxymethyl Glycals

  摘要：

  C-2-Methylene O- and C-glycosides are readily synthesized from C-2-acetoxymethyl glycals using Nafion-H(R), montmorillonite K-10, LiClO4 (0.07 M) in dichloromethane and Pd(PPh3)(4) as catalysts. Exclusive alpha or beta selectivities have been observed with various primary, secondary and tertiary alcohols, phenols and diethyl malonate. Further, C-2-acetoxymethyl glycals are also converted into corresponding alpha -methylene-delta -valerolactones in good yields in one step using m-CPBA in the presence of BF3. Et2O. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(00)00775-4
• 作为产物：
  描述：

  N,N-二甲基甲酰胺 、 3,4,6-三-O-甲基-D-葡萄糖醛 在 三氯氧磷 、 水 、 sodium acetate 作用下， 反应 15.0h， 以77%的产率得到1,5-anhydro-2-deoxy-2-formyl-3,4,6-tri-O-methyl-D-arabino-hex-1-enitol
  参考文献：
  名称：

  VO（acac）2 -CeCl 3复合催化剂及其自聚集纳米结构材料的合成基于乙二醇的手性苯并咪唑

  摘要：

  已开发出VO（acac）2 -CeCl 3组合催化剂，用于在温和的反应条件下进行化学选择性环缩合和氧化，以合成新型光学纯化合物2-（2'- C -3'，4'，6'-三-O-苄基/甲基-糖基）-1 H-苯并咪唑。它涉及一种操作简单的合成方案，可有效地高产率地合成多种手性苯并咪唑，而不会形成不希望的1,2-二取代和假糖副产物。钒（V）被发现是化学过程中的活性氧化剂，通过紫外吸收光谱法对其进行了研究。高阶一维低分子量有机纳米结构材料是通过手性纳米级结构单元的纳米结晶而制备的。糖基手性苯并咪唑的B3LYP / 6-31G **理论水平的理论计算显示出1 H-蒽的平面几何形状[1,2- d]咪唑-6,11-二酮部分，负责强烈的自聚集，生成超长纳米结构材料。我们还发现理论结果与2D-NOESY实验中的实验观察结果之间有很好的一致性。还报道了固体纳米结构材料的光物理性质。

  DOI：

  10.1021/jo901458k

文献信息

• Acetic Anhydride–Acetic Acid as a New Dehydrating Agent of Aldoximes for the Preparation of Nitriles: Preparation of 2-Cyanoglycals
  作者：Henok H. Kinfe、Tommy F. Mabasa、Jackie Mabasa、Mthokozisi Simelane、Banele Vatsha、Banothile C.E. Makhubela

  DOI：10.1055/s-0040-1708007

  日期：2020.6

  Herein, we report a combination of Ac2O and AcOH as new and efficient dehydrating agent of aldoximes for the synthesis of 2-cyanoglycals. In comparison to the conventional dehydrating system of Ac2O-base (such as NaOH, NaOAc and K2CO3), the current protocol provides superior yields and faster reaction rates. The scope and limitations of the dehydrating system are investigated.

  Glycals 是一种 1,2-不饱和碳水化合物，是合成各种支架的通用构件。尽管它们有可能在面向多样性的合成中用作合适的前体，但在合成和衍生化方面对 2-氰基糖的探索较少。在此，我们报告了 Ac2O 和 AcOH 的组合作为用于合成 2-氰基的新型高效醛肟脱水剂。与传统的 Ac2O 碱脱水系统（如 NaOH、NaOAc 和 K2CO3）相比，当前的协议提供了更高的产量和更快的反应速率。研究了脱水系统的范围和局限性。
• Regioselective and reductive cleavage of allyl ethers by NaBH4–HOAc
  作者：Zi-Ping Lin、Fung Fuh Wong、Yen-Bo Chen、Chun-Hung Lin、Min-Tsang Hsieh、Jin-Cherng Lien、Yin-Hsuan Chou、Hui-Chang Lin

  DOI：10.1016/j.tet.2013.03.020

  日期：2013.5

  NaBH4 in HOAc led to unexpected reductive cleavage of allyl ether, i.e., the hydrodealkoxylation took place to produce the corresponding 3-deoxy-β-enaminals. In contrast, the reaction of β-enaminals with Zn/HOAc performed H4-elimination to afford a diene product. The result was attributed to the formation of a common eneiminium ion intermediate, and the different reduction reactivity.

  通过C 2-甲酰基糖与伯胺的反应，成功地合成了β-香精，收率良好。随后在HOAc中与NaBH 4反应导致烯丙基醚的意外还原裂解，即发生加氢脱烷氧基化以产生相应的3-脱氧-β-烯胺。相反，β-烯醛与Zn / HOAc的反应进行H 4消除，得到二烯产物。结果归因于常见的亚胺鎓离子中间体的形成，以及不同的还原反应性。
• Synthesis and evaluation of pyrazolo[3,4-b]pyridines and its structural analogues as TNF-α and IL-6 inhibitors
  作者：Sandip B. Bharate、Tushar R. Mahajan、Yogesh R. Gole、Mahesh Nambiar、T.T. Matan、Asha Kulkarni-Almeida、Sarala Balachandran、H. Junjappa、Arun Balakrishnan、Ram A. Vishwakarma

  DOI：10.1016/j.bmc.2008.06.042

  日期：2008.8

  In the present article, we have synthesized three different series of pyrazolo[3,4-b]pyridines and their structural analogues using novel synthetic strategy involving one-pot condensation of 5,6-dihydro-4H-pyran-3-carbaldehyde/2-formyl-3,4,6-tri-O-methyl-D-glucal/chromone -3-carbaldehyde with heteroaromatic amines. All synthesized compounds were evaluated for their anti-inflammatory activity against

  在本文中，我们使用涉及一锅缩合5,6-二氢-4H-吡喃-3-甲醛/ 2的新颖合成策略，合成了三个不同系列的吡唑并[3,4-b]吡啶及其结构类似物-甲酰基-3,4,6-三-O-甲基-D-葡萄糖/色酮-3-甲醛与杂芳族胺。评价所有合成的化合物对TNF-α和IL-6的抗炎活性。在筛选出的28种化合物中，有40、51、52和56在10 microM浓度下显示出对IL-6有希望的活性，并具有60-65％的抑制率。其中51、52和56表现出有效的IL-6抑制活性，IC（50）分别为0.2、0.3和0.16 microM。浓度> 100 microM时，化合物56在CCK-8细胞中无细胞毒性。
• Glycosidation of 3,4,6-Tri-<i>O</i>-Benzyl-2-Ethenyl-D-Glucal – A Route to 2-<i>C</i>-(β-Methyl)Methylene Glycosides
  作者：Ben-Ami Feit、Idil Kasuto Kelson、Anke Gerull、Sarah Abramson、Richard R. Schmidt

  DOI：10.1080/07328300008544109

  日期：2000.1

  Monosaccharidic and disaccharidic 2-C-(beta-methyl)methylene glycosides were synthesized by an electrophilic conjugate addition reaction of ROH-type compounds in the presence of Ph3+PH Br- to 2-ethenyl-3,4,6-tri-O-benzyl-D-glucal 1, functioning as a model glycosyl donor. This 2-vinyl glucal derivative represents a series of 2-vinyl, and 2-butadienyl glycals, prepared by Wittig-type methylenation of pyranosidic conjugated enals, derived from glucal, galactal and lactal. The exo-(beta-methyl)methylene group paves the way for further chemical transformations.
• Vilsmeier-haack reactoin of glycals-a short route to C-2-formyl glycals
  作者：N.G. Ramesh、K.K. Balasubramanian

  DOI：10.1016/s0040-4039(00)79402-0

  日期：1991.7

  A short and straightforward route has been accomplished for the synthesis of C-2-formyl glycals by a Vilsmeier-Haack reaction of glycals.