3-deoxy-1,2:5,6-di-O-isopropylidene-3-isothiocyanato-3-C-vinyl-α-D-glucofuranose | 195315-66-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-deoxy-1,2:5,6-di-O-isopropylidene-3-isothiocyanato-3-C-vinyl-α-D-glucofuranose
• 英文别名: (3aR,5S,6S,6aR)-5-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-6-ethenyl-6-isothiocyanato-2,2-dimethyl-5,6a-dihydro-3aH-furo[2,3-d][1,3]dioxole
• CAS: 195315-66-3
• 化学式: C₁₅H₂₁NO₅S
• 分子量: 327.401
• InChiKey: MSJMDCQJXWXJTO-OVKLUEDNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  90.6
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  3-deoxy-1,2:5,6-di-O-isopropylidene-3-isothiocyanato-3-C-vinyl-α-D-glucofuranose 在 camphor-10-sulfonic acid 作用下， 以 甲醇 、 乙醚 为溶剂， 反应 5.5h， 生成 3-deoxy-3-(N-cyclopentylthiocarboxamido)-1,2-O-isopropylidene-3-C-vinyl-α-D-glucofuranose
  参考文献：
  名称：

  Creation of quarternary stereocentres via [3,3]-sigmatropic rearrangement of allylic thiocyanates. A synthetic approach to (+)-myriocin

  摘要：

  A stereoselective approach to the advanced precursor of (+)-myriocin, 3-deoxy-1,2:5,6-di-O-isopropylidene-3-methoxycarbonylamino-alpha-D-glucofuranose 3-C-carboxylic acid, via the [3,3]-sigmatropic rearrangement of allylic thiocyanates prepared from D-glucose is presented. From the observed results, supported by DFT calculations, we can conclude that the [3,3]-sigmatropic rearrangement of the thiocyanato group in allylic hexofuranosides is strongly influenced by the steric interaction of the 1,2-O-isopropylidene group in the transition states. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2006.06.032
• 作为产物：
  描述：

  3-deoxy-1,2:5,6-di-O-isopropylidene-3-C-(Z)-(2-thiocyanatoethylidene)-α-D-glucofuranose 以 邻二甲苯 为溶剂， 反应 4.0h， 以85%的产率得到3-deoxy-1,2:5,6-di-O-isopropylidene-3-isothiocyanato-3-C-vinyl-α-D-glucofuranose
  参考文献：
  名称：

  Creation of quarternary stereocentres via [3,3]-sigmatropic rearrangement of allylic thiocyanates. A synthetic approach to (+)-myriocin

  摘要：

  A stereoselective approach to the advanced precursor of (+)-myriocin, 3-deoxy-1,2:5,6-di-O-isopropylidene-3-methoxycarbonylamino-alpha-D-glucofuranose 3-C-carboxylic acid, via the [3,3]-sigmatropic rearrangement of allylic thiocyanates prepared from D-glucose is presented. From the observed results, supported by DFT calculations, we can conclude that the [3,3]-sigmatropic rearrangement of the thiocyanato group in allylic hexofuranosides is strongly influenced by the steric interaction of the 1,2-O-isopropylidene group in the transition states. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2006.06.032

文献信息

• Novel carbohydrate-based thioureas as organocatalysts for asymmetric michael addition of 1,3-dicarbonyl compounds to nitroolefins
  作者：Róbert Rončák、Monika Tvrdoňová、Jozef Gonda、Ján Elečko

  DOI：10.1016/j.tet.2020.131339

  日期：2020.7

  A series of novel carbohydrate-derived thioureas were synthesized and examined as catalysts for the asymmetric Michael addition of symmetrical 1,3-dicarbonyl compounds, including dimethyl malonate, to several trans-β-nitrostyrenes. High enantioselectivities (up to 94% ee) as well as high yields (up to 98%) were attained using a bifunctional organocatalyst bearing a cinchona-based alkaloid unit.

  一系列新颖的碳水化合物衍生的硫脲的合成和研究作为催化剂用于不对称迈克尔加成对称1,3-二羰基化合物，包括丙二酸二甲酯，对几个反式- β -nitrostyrenes。使用带有金鸡纳生物碱单元的双功能有机催化剂，可以获得高对映选择性（最高94％ee）和高产率（最高98％）。
• Stereoselective synthesis of a novel branched-chain (1S,2R,6R,7S)-7a-(hydroxymethyl)-1,2,6,7-tetrahydroxypyrrolizidine
  作者：Jozef Gonda、Ján Elečko、Miroslava Martinková、Martin Fábian

  DOI：10.1016/j.tetlet.2016.05.070

  日期：2016.6

  An efficient and highly stereoselective approach towards a new type of branched-chain pentahydroxylated pyrrolizidine 7 from a d-glucose isothiocyanate scaffold has been developed. The key features of this strategy are the construction of a diene-substrate foldamer possessing an amino functional group followed by subsequent ring-closing metathesis, an intramolecular cyclisation readily induced by regioselective

  已经开发了一种从d-葡萄糖异硫氰酸酯支架向新型支链五羟基化吡咯烷并7的高效且高度立体选择性的方法。该策略的关键特征是：构建具有氨基官能团的二烯-底物折叠剂，随后进行闭环复分解；通过区域选择性甲苯磺酸化容易地诱导的分子内环化反应，以建立吡咯嗪烷单元；以及高度非对映选择性，底物控制的二羟基化反应。
• Design and synthesis of novel carbohydrate-amino acid hybrids and their antioxidant and anti-β-amyloid aggregation activity
  作者：Monika Tvrdoňová、Barbora Borovská、Aneta Salayová、Róbert Rončák、Peter Michalčin、Zuzana Bednáriková、Zuzana Gažová

  DOI：10.1016/j.bioorg.2023.106636

  日期：2023.8

  differed between the studied peptides. While the destruction activity of the compounds on the HEW lysozyme amyloid fibrils was negligible, the effect on Aβ40 amyloid fibrils was significantly higher. Furanoid sugar α-amino acid 1 and its dipeptide derivatives 8 (Trp-Trp) and 11 (Trp-Tyr) were the most potent anti-Aβ fibrils compounds. The antioxidant properties of synthesized compounds were estimated

  在此，我们报道了通过将芳香族氨基酸和二肽与异硫氰酸基官能化的呋喃核糖环偶联制备的新型呋喃糖氨基酸和硫脲的合成。由于碳水化合物衍生的结构具有许多生物活性，合成的化合物被评估为抗淀粉样蛋白和抗氧化剂。所研究化合物的抗淀粉样蛋白活性是根据它们破坏本质上无序的 Aβ 40肽和球状鸡蛋清 (HEW) 溶菌酶的淀粉样蛋白原纤维的潜力进行评估的。化合物的破坏效率因所研究的肽而异。虽然化合物对 HEW 溶菌酶淀粉样原纤维的破坏活性可以忽略不计，但对 Aβ 40的影响淀粉样原纤维显着升高。呋喃糖α-氨基酸1及其二肽衍生物8 (Trp-Trp) 和11 (Trp-Tyr) 是最有效的抗 Aβ 原纤维化合物。合成化合物的抗氧化特性通过三种互补的体外测定（DPPH、ABTS 和 FRAP）进行评估。与 DPPH 试验相比，ABTS 试验对于评估所有测试化合物的自由基清除活性最为敏感。根据存在的氨基酸，检测到芳香族
• Stereocontrol by intrinsic antiparallel double repulsion on diacetone-D-glucose template. Diastereoselective synthesis of 3(S)-isothiocyanato-3-deoxy-3-C-vinyl glucose via (3,3)-sigmatropic rearrangement of allylic thiocyanates
  作者：Jozef Gonda、Miroslava Bednárikova

  DOI：10.1016/s0040-4039(97)01246-x

  日期：1997.8

  A stereoselective synthesis of the branched-chain sugar 3(S)-isothiocyanato-3-deoxy-3-C-vinyl glucose via (3,3)-sigmatropic rearrangement of allylic thiocyanates prepared from D-glucose is presented. The side chain at C-4 of the substrates 4-Z, 4-E and 8-E is not a decisive factor for stereocontrol in the (3,3)-sigmatropic rearrangement of allylic thiocyanates, and the 1,2-O-isopropylidene group in each isomer profoundly affects the direction of the rearrangement. (C) 1997 Elsevier Science Ltd.