3-O-benzyl-1,2:5,6-di-O-isopropylidene-α-D-gulofuranoside | 23885-38-3

• 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: 3-O-benzyl-1,2:5,6-di-O-isopropylidene-α-D-gulofuranoside
• 英文别名: 3-O-benzyl-1,2:5,6-di-O-isopropylidene-α-D-gulofuranose；(3aR,5S,6R,6aR)-6-(Benzyloxy)-5-((R)-2,2-dimethyl-1,3-dioxolan-4-yl)-2,2-dimethyltetrahydrofuro[2,3-d][1,3]dioxole；(3aR,5S,6R,6aR)-5-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-6-phenylmethoxy-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxole
• CAS: 23885-38-3
• 化学式: C₁₉H₂₆O₆
• 分子量: 350.412
• InChiKey: ZHFVGOMEUGAIJX-ZHCJQAHYSA-N

物化性质

• 沸点：
  422.6±45.0 °C(Predicted)
• 密度：
  1.21±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  25
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  55.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3-O-benzyl-1,2:5,6-di-O-isopropylidene-α-D-gulofuranoside 在 草酰氯 、 Dowex 50W 、 sodium hydride 、 二异丁基氢化铝 、 对甲苯磺酸 、 二甲基亚砜 、 三乙胺 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 、 paraffin 为溶剂， 反应 36.5h， 生成 (2S,3R,4R,5R,6R)-5,6-dimethoxy-3,4-bis(phenylmethoxy)oxane-2-carbaldehyde
  参考文献：
  名称：

  An enantioselective synthesis of bengamide E

  摘要：

  DOI：

  10.1021/jo00044a053
• 作为产物：
  描述：

  1,2:5,6-di-O-isopropylidene-α-D-ribo-hexofuranos-3-ulose-hydrate 在 Rh/Al₂O₃ 吡啶 、 氢气 、 sodium methylate 、 四丁基碘化铵 、 sodium hydride 作用下， 以 四氢呋喃 、 乙酸乙酯 为溶剂， 20.0~80.0 ℃ 、5.0 MPa 条件下， 反应 8.83h， 生成 3-O-benzyl-1,2:5,6-di-O-isopropylidene-α-D-gulofuranoside
  参考文献：
  名称：

  （D）-葡萄糖向（D）-葡萄糖的双重差向异构化和（D）-木糖-咪唑并哌啶子糖的合成

  摘要：

  铑/氧化铝催化的已知烯醇-乙酸酯7的顺式氢化反应是定量进行的，并且具有完全的立体选择性，从而生成D-古洛糖衍生物8。几个反应步骤允许将8转化为目标D-木糖-咪唑并哌啶子糖ent - 4分子，即已知咪唑糖4的对映异构体。

  DOI：

  10.1016/s0040-4039(99)01003-5

文献信息

• Stereoisomeric Imidazolo-Pentoses − Synthesis, Chiroptical Properties, and Evaluation as Glycosidase Inhibitors
  作者：Théophile Tschamber、Hervé Siendt、Arnaud Boiron、François Gessier、Dariusz Deredas、Andrzej Frankowski、Sylviane Picasso、Heinz Steiner、Anne-Marie Aubertin、Jacques Streith

  DOI：10.1002/1099-0690(200104)2001:7<1335::aid-ejoc1335>3.0.co;2-z

  日期：2001.4

  The syntheses of all four imidazolo-piperidino-pentoses in the L-series ent-2 to ent-5, and of three out of the four possible stereomers in the D-series 3, 4, and 5, are reported. The linear imidazolo sugar precursors were prepared, either by double condensation of formamidine with protected aldohexoses, or by nucleophilic addition of a lithiated imidazole derivative to protected aldotetroses. Cyclisation

  报告了 L 系列 ent-2 至 ent-5 中所有四种咪唑并哌啶基戊糖的合成，以及 D 系列 3、4 和 5 中四种可能立体异构体中三种的合成。线性咪唑并糖前体通过甲脒与受保护的己醛糖的双重缩合或通过锂化咪唑衍生物与受保护的醛四糖的亲核加成来制备。这些线性咪唑并碳水化合物的环化是通过分子内 SN2 反应进行的。然后对目标分子进行脱保护。四对相反的对映体在其 CD 光谱中显示出明显的镜像型棉花效应。D 系列的所有立体异构体都显示负旋光度 ([α]D)，而 L 系列的立体异构体显示正旋光度。八种咪唑并糖均不抑制 HIV-1 的复制。根据 Michaelis-Menten 动力学确定，其中一些被证明是相当有选择性的，但只是中等有效的 α-糖苷酶抑制剂。
• A diastereoselective C–C bond formation at C-5 of d-gulose. A convenient approach to (5S)-5-C-alkyl-β-l-lyxo-hexofuranoses
  作者：Jozef Gonda、Dávid Maliňák、Margaréta Kováčová、Miroslava Martinková、Martin Walko

  DOI：10.1016/j.tetasy.2013.10.003

  日期：2013.12

  A flexible approach to the stereoselective synthesis of (5S)-5-C-methyl- and (5S)-5-C-ethyl-beta-L-lyxo-hexofuranoses 15a, 22 starting from 1,2:5,6-di-O-isopropylidene-alpha-D-gulofuranose 3 as the source of chirality is described. The corresponding C-5 alkyl groups were introduced via a Wittig olefination followed by Pd/C-mediated hydrogenation of the conformationally restricted alkenes in a highly diastereoselective manner. (C) 2013 Elsevier Ltd. All rights reserved.
• Titanocene Dihalides and Ferrocenes Bearing a Pendant α-<scp>d</scp>-Xylofuranos-5-yl or α-<scp>d</scp>-Ribofuranos-5-yl Moiety. Synthesis, Characterization, and Cytotoxic Activity
  作者：Tomáš Hodík、Martin Lamač、Lucie Červenková Št’astná、Jindřich Karban、Lucie Koubková、Roman Hrstka、Ivana Císařová、Jiří Pinkas

  DOI：10.1021/om500200r

  日期：2014.4.28

  Titanocene dichlorides of general formula [(eta(5)-C5H5)(eta(5)-C5H4R)TiCl2] (where R = 5-deoxy-1,2-di-O-isopropylidene-3-O-benzyl-alpha-D-xylofuranos-5-yl (Xylf) (8a); R = 5-deoxy-1,2-di-O-isopropylidene-3-O-benzyl-alpha-D-ribofuranos-5-yl (Ribf) (8b)) and [(eta(5)-C5H4R)(2)TiCl2] (R = Xylf (9a); R = Ribf (9b)) were prepared by reaction of the corresponding lithium cyclopentadienides 7a,b with an equimolar amount of [(eta(5)-C5H5)TiCl3] or a 0.5 mol amount of [TiCl4(THF)(2)]. Titanocene difluorides of the general formula [(eta(5)-C5H4R1)(eta(5)-C5H4R2)TiF2] (R-1 = H and R-2 = Ribf (10); R-1 = R-2 = Xylf (11a); R-1 = R-2 = Ribf (11b)) were obtained by fluorination of the corresponding titanocene dichlorides 8b and 9 with the fluorinating agent 2-(CH2NMe2)C6H4-kappa C,N}(n-Bu)(2)SnF in high yields. Alternatively, complexes 11 were prepared in a straightforward way by direct reaction of [TiF4(THF)(2)] with 2 equiv of the corresponding lithium cyclopentadienide 7a,b. Ferrocene complexes [(eta(5)-C5H4R)(2)Fe] (R = Xylf (12a); R = Ribf (12b)) were synthesized by metathesis of 2 equiv of lithium cyclopentadienide 7a,b and 1 equiv of anhydrous FeCl2. Deprotection of the benzyl group in ferrocenes 12 proceeded cleanly by a catalytic hydrogenation on Pd/C and afforded the ferrocene diols [(eta(5)-C3H4R)(2)Fe] (R = 5-deoxy-1,2-di-O-isopropylidene-alpha-D-xylofuranos-5-yl (Xylf-OH) (14a); R = 5-deoxy-1,2-di-O-isopropylidene-alpha-D-ribofuranos-5-yl (Ribf-OH) (14b)). A scaled up benzyl deprotection with Et3SiH as a hydrogen source led to the replacement of only one benzyl group, which gave the ferrocene alcohol [(eta(5)-C5H4R1)(eta(5)-C5H4R2)Fe] (R-1 = Xylf and R-2 = Xylf-OH (13)). The prepared complexes were characterized by elemental analysis, melting point determination, NMR, IR, and ESI-MS, and the molecular structure of 9b was determined by X-ray diffraction analysis. The cytotoxic activity of complexes 8-14 against A2780 and A2780cis cancer cells was evaluated by MTT tests. Titanocene difluorides 10 and 11 and ferrocene diol 14a showed cytotoxicity against A2780 cells in the medium to low micromolar range, while the most active species, 11b, displayed about 40% higher cytotoxicity against A2780cis in comparison to a cisplatin standard.
• An enantioselective synthesis of bengamide E
  作者：Hisakazu Kishimoto、Hiroshi Ohrui、Hiroshi Meguro

  DOI：10.1021/jo00044a053

  日期：1992.8
• Improved double epimerisation of (D)-glucose into (D)-gulose and the synthesis of (D)-xylo-imidazolopiperidinose
  作者：Hervé Siendt、Théophile Tschamber、Jacques Streith

  DOI：10.1016/s0040-4039(99)01003-5

  日期：1999.7

  Rhodium/alumina catalysed cis-hydrogenation of the known enol-acetate 7 proceeded quantitatively and with complete stereoselectivity leading to the D-gulose derivative 8. Several reaction steps permitted transformation of 8 into the target D-xylo-imidazolopiperidinose ent-4 molecule, i.e. the enantiomer of the already known imidazolo-sugar 4.

  铑/氧化铝催化的已知烯醇-乙酸酯7的顺式氢化反应是定量进行的，并且具有完全的立体选择性，从而生成D-古洛糖衍生物8。几个反应步骤允许将8转化为目标D-木糖-咪唑并哌啶子糖ent - 4分子，即已知咪唑糖4的对映异构体。