4-((R)-2,2-dimethyl-1,3-dioxolan-4-yl)-6-methoxy-2,2-dimethyltetrahydrofuro[3,4-d][1,3]dioxole | 26255-73-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-((R)-2,2-dimethyl-1,3-dioxolan-4-yl)-6-methoxy-2,2-dimethyltetrahydrofuro[3,4-d][1,3]dioxole
• 英文别名: methyl 2,3:5,6-di-O-isopropylidene-α-D-mannofuranoside；Methyl-2,3:5,6-di-O-isopropyliden-α-D-mannofuranosid；Methyl 2,3:5,6-di-O-isopropylidene-alpha-D-mannofuranoside；(3aS,4S,6R,6aS)-6-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-4-methoxy-2,2-dimethyl-3a,4,6,6a-tetrahydrofuro[3,4-d][1,3]dioxole
• CAS: 26255-73-2
• 化学式: C₁₃H₂₂O₆
• 分子量: 274.314
• InChiKey: XNLQMLBTTKKQOD-UVOCVTCTSA-N

物化性质

• 沸点：
  326.8±42.0 °C(Predicted)
• 密度：
  1.20±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  4-((R)-2,2-dimethyl-1,3-dioxolan-4-yl)-6-methoxy-2,2-dimethyltetrahydrofuro[3,4-d][1,3]dioxole 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) sodium periodate 、 正丁基锂 、 silica gel 、 溶剂黄146 、 三苯基膦 、 锌 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 甲苯 为溶剂， 反应 37.25h， 生成 2-[(3aS,4S,6R,6aS)-4-methoxy-2,2-dimethyl-3a,4,6,6a-tetrahydrofuro[3,4-d][1,3]dioxol-6-yl]anthracene-9,10-dione
  参考文献：
  名称：

  A New Versatile Strategy for C-Aryl Glycosides

  摘要：

  A versatile strategy involving a sequential intermolecular enyne metathesis of C-alkynyl glycosides with ethylene, Diels-Alder, and aromatization reactions is successfully developed to provide a range of C-aryl glycosides.

  DOI：

  10.1021/ol0701159
• 作为产物：
  描述：

  2,3,5,6-di-O-isopropylidene-D-mannofuranose 在 四氯化锡 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 24.0h， 生成 4-((R)-2,2-dimethyl-1,3-dioxolan-4-yl)-6-methoxy-2,2-dimethyltetrahydrofuro[3,4-d][1,3]dioxole
  参考文献：
  名称：

  A new, stereospecific method for the synthesis of 2,3:5,6-di-O-isopropylidene-α-D-mannofuranosides

  摘要：

  DOI：

  10.1016/s0008-6215(00)82601-4

文献信息

• Selective radical-chain epimerisation at electron-rich chiral tertiary C–H centres using thiols as protic polarity-reversal catalysts
  作者：Hai-Shan Dang、Brian P. Roberts、Derek A. Tocher†

  DOI：10.1039/b103558b

  日期：——

  Radical-chain epimerisation at chiral tertiary CH centres adjacent to ethereal oxygen atoms can be brought about in the presence of thiols, the function of which is to act as protic polarity-reversal catalysts for hydrogen-atom transfer between pairs of nucleophilic α-alkoxyalkyl radicals. The viability of the method is demonstrated by epimerisation of a series of simple molecules that contain two chiral centres and then the procedure is applied to more complex carbohydrate-based systems, where it is possible to convert a readily available diastereoisomer into a rarer one in a straightforward manner. Of necessity, epimerisation always proceeds in the direction of thermodynamic equilibrium and, in general, the results obtained are in accord with the predictions of molecular mechanics calculations using the MMX force-field. When the required isomer is less stable than the starting diastereoisomer, thiol-catalysed epimerisation of a suitable derivative of the parent can provide a means to obtain the desired compound in satisfactory yield, after deprotection of the epimerised derivative. This strategy is demonstrated for the conversion of trans-cyclohexane-1,2-diol into the less stable cis-isomer and for related contra-thermodynamic isomerisation of some carbohydrates, as well as for the conversion of meso-1,2-diphenylethane-1,2-diol into the dl-form. Thiol-catalysed epimerisation at a CH centre adjacent to an ether-oxygen atom is much faster than at a similar centre adjacent to an amido-nitrogen atom, a result that can be understood in terms of the importance of polar effects on the rate of abstraction of hydrogen by electrophilic thiyl radicals.

  硫醇的作用是作为亲核δ-烷氧基烷基自由基对之间氢原子转移的原生极性反转催化剂，可以在邻近乙氧基原子的手性三级 CH 中心实现自由基链表并化。通过对一系列含有两个手性中心的简单分子进行外延二聚化，证明了该方法的可行性，然后将该程序应用于更复杂的基于碳水化合物的体系，在这些体系中，可以通过直接的方式将容易获得的非对映异构体转化为较罕见的非对映异构体。必要时，二聚化总是朝着热力学平衡的方向进行，一般来说，所获得的结果与使用 MMX 力场进行分子力学计算的预测结果一致。当所需异构体的稳定性低于起始非对映异构体时，可采用巯基催化母体的适当衍生物进行外延化反应，在对外延化衍生物进行脱保护处理后，以令人满意的收率获得所需化合物。这种策略在反式-1,2-环己烷二醇转化为稳定性较差的顺式异构体、某些碳水化合物的相关逆热力学异构化以及介-1,2-二苯基乙烷-1,2-二醇转化为 dl-形式时得到了验证。邻近醚氧原子的 CH 中心在硫醇催化下的缩合反应要比邻近酰胺氮原子的类似中心快得多，这一结果可以从极性效应对亲电巯基取氢速率的重要性角度来理解。
• Crown Ether Catalyzed<i>O</i>-Alkylation of Carbohydrates and Nucleosides
  作者：Michel Bessodes、Jila Shamsazar、Kostas Antonakis

  DOI：10.1055/s-1988-27640

  日期：——

  Carbohydrate derivatives as well as nucleosides are readily alkylated with different alkyl halides in tetrahydrofuran using potassium hydroxide in the presence of crown ether.

  在四氢呋喃中，使用氢氧化钾并在冠醚的存在下，碳水化合物衍生物和核苷很容易与不同的烷基卤化物发生烷基化反应。
• The endocyclic oxygen atom of d-mannopyranose is involved in its binding to pradimicins
  作者：Yasunori Watanabe、Fumiya Yamaji、Makoto Ojika、Takahiro Sugawara、Dai Akase、Misako Aida、Yasuhiro Igarashi、Yukishige Ito、Yu Nakagawa

  DOI：10.1016/j.tetlet.2019.151530

  日期：2020.2

  Methyl 5-thio-α-D-mannopyranoside (1) and six inositols were evaluated for their ability to bind to pradimicins (PRMs) via molecular modeling and three binding assays. In all the experiments, the binding affinity of 1 was slightly lower than that of methyl α-D-mannopyranoside (Man-OMe) and inositols hardly bound to PRMs. These results indicate that the endocyclic oxygen atom of Man-OMe is involved

  通过分子建模和三种结合试验评估了甲基5-硫代-α-D-甘露吡喃糖苷（1）和6种肌醇与大黄素（PRM）结合的能力。在所有的实验中，结合亲和力1略低于该甲基α-d-D-吡喃甘露糖苷（曼-OME）和肌醇的几乎不结合的PRM。这些结果表明Man-OMe的环内氧原子参与了其与PRM的结合。
• Synthesis and Structural Analysis of 5-Deoxy-5-[(<i>R</i>)- and (<i>S</i>)-methylphosphinyl]-α,β-D-manno- and -L-gulopyranoses
  作者：Tadashi Hanaya、Katsuhiko Ohmori、Hiroshi Yamamoto、Margaret-Ann Armour、Alan M. Hogg

  DOI：10.1246/bcsj.63.1174

  日期：1990.4

  Methyl 5,6-dideoxy-2,3-O-isopropylidene-6-nitro-α-D-lyxo-hex-5-enofuranoside (10) was prepared from D-mannose in 7 steps. Addition of methyl methylphosphinate to 10, followed by the catalytic hydrogenation and diazotization, afforded methyl 5-deoxy-2,3-O-isopropylidene-5-[(methoxy)methylphosphinyl]-α-D-lyxo-hexofuranoside, which was then converted into 6-O-triphenylmethyl and 6-O-tetrahydropyranyl

  甲基 5,6-dideoxy-2,3-O-isopropylidene-6-nitro-α-D-lyxo-hex-5-enofuranoside (10) 由 D-甘露糖分 7 个步骤制备。甲基次膦酸甲酯加成到 10，然后催化氢化和重氮化，得到甲基 5-deoxy-2,3-O-isopropylidene-5-[(甲氧基)methylphosphinyl]-α-D-lyxo-hexofuranoside，然后将其转化转化为 6-O-三苯甲基和 6-O-四氢吡喃基衍生物 (14, 15)。通过用二氢双（2-甲氧基乙氧基）铝酸钠还原，然后酸水解，14 和 15 都提供了 D-吡喃甘露糖（连同小比例的 L-吡喃葡萄糖），其具有甲基亚膦基代替环氧。这些被转化为 1,2,3,4,6-penta-O-乙酰衍生物，其结构和构象由光谱学确定。
• Stereoselective synthesis of (−)-protulactone A
  作者：Qingwei Lv、Caizhu Chang、Yong Li、Yuguo Du、Jun Liu

  DOI：10.1016/j.tet.2020.131290

  日期：2020.6

  An efficient stereoselective synthesis of (−)-protulactone A was established in 9 steps and 14.7% overall yields using d-mannose as starting material. The key steps of our synthesis involved one-pot deprotection/lactonization/Michael addition reaction/acetalization and 1, 3-chelated controlled stereoselective addition.

  以d-甘露糖为起始原料，通过9个步骤建立了有效的立体选择性合成（-）-丙内酯A，总产率为14.7％。我们合成的关键步骤涉及一锅脱保护/内酰胺化/迈克尔加成反应/缩醛化和1，3螯合的受控立体选择性加成。