3,4:5,6-di-O-isopropylidene-D-glucose diethyl dithioacetal | 4435-02-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3,4:5,6-di-O-isopropylidene-D-glucose diethyl dithioacetal
• 英文别名: 3,4:5,6-Di-O-isopropyliden-D-glucose-diethyl-dithioacetal；2.3;5.6-Di-iopropyliden-D-glucose-diethyl-thioacetal；(1R)-1-[(4R,5R)-5-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-bis(ethylsulfanyl)ethanol
• CAS: 4435-02-3
• 化学式: C₁₆H₃₀O₅S₂
• 分子量: 366.543
• InChiKey: UERSREDSHSAYDR-FDYHWXHSSA-N

物化性质

• 沸点：
  472.8±40.0 °C(Predicted)
• 密度：
  1.147±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  23
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  108
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  3,4:5,6-di-O-isopropylidene-D-glucose diethyl dithioacetal 在 palladium on activated charcoal 氢气 、 mercury dichloride 、 mercury(II) oxide 作用下， 以 水 、 乙酸乙酯 、 丙酮 、 苯 为溶剂， 25.0 ℃ 、101.33 kPa 条件下， 反应 5.08h， 生成 methyl 2,3-dideoxy-5,6:7,8-di-O-isopropylidene-D-gluco-octonate
  参考文献：
  名称：

  A synthesis of 3-deoxy-D-gluco-oct-2-ulosonic acid

  摘要：

  Acyclic 2:3,5:6- and 3:4,5:6-di-O-isopropylidene-D-glucoses have been converted by four reactions involving a Wittig chain homologation, a catalytic hydrogenation, an acid hydrolysis and an acetonation into 2,3-dideoxy-5:6,7:8-di-O-isopropylidene-D-gluco-octono-1,4-lactone which underwent a Wasserman reaction and then a hydrolysis to yield 3-deoxy-D-gluco-oct-2-ulosonic acid, isolated as its ammonium salt 2.

  DOI：

  10.1016/s0957-4166(00)80388-2
• 作为产物：
  描述：

  D-葡萄糖-二乙基缩硫醛 、 2,2-二甲氧基丙烷 在 盐酸 作用下， 以 丙酮 为溶剂， 反应 0.5h， 以22%的产率得到3,4:5,6-di-O-isopropylidene-D-glucose diethyl dithioacetal
  参考文献：
  名称：

  Structure–activity relationship studies on acremomannolipin A, the potent calcium signal modulator with a novel glycolipid structure 2: Role of the alditol side chain stereochemistry

  摘要：

  Five alditol analogs 1b-1f of a novel glycolipid acremomannolipin A (1a), the potential Ca2+ signal modulator isolated from Acremonium strictum, were synthesized by employing a stereoselective beta-mannosylation of appropriately protected mannose with five hexitols with different stereochemistry, and their potential on modulating Ca2+ signaling were evaluated. All these analogs were more potent compared to the original compound 1a, and proved that mannitol stereochemistry of 1a was not critical for the potent calcium signal modulating. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmc.2013.12.052

文献信息

• The rearrangement of mono-O-isopropylidene derivatives of aldose diethyl dithioacetals
  作者：T. Bruce Grindley、Chandra Wickramage

  DOI：10.1016/0008-6215(87)80272-0

  日期：1987.9

  -Isopropylidene- d -mannose diethyl dithioacetal was also prepared directly from d -mannose diethyl dithioacetal. Consistent ratios of product to starting material indicated that the 4,5- trans -disubstituted 2,2-dimethyl-1,3-dioxolane products are ∼1.2 kcal.mol −1 more stable than the 4-substituted 2,2-dimethyl-1,3-dioxolane starting-materials. Reaction of d -glucose diethyl dithioacetal with an excess of 2-methoxypropene

  摘要研究了一些醛糖二乙基二硫缩醛在N，N-二甲基甲酰胺中的酸催化端基-O-异亚丙基衍生物的重排。d-阿拉伯糖和d-木糖二乙基二硫缩醛的4，5-O-异亚丙基衍生物分别重排至2，3-和2，3-和3，4-和3，4-O-异亚丙基衍生物的混合物。d-半乳糖，d-甘露糖和d-葡萄糖的5,6- O-异亚丙基衍生物重新排列为4,5、3,4-和2,3-和3,4-O的混合物-异亚丙基衍生物。通过交叉实验，并考虑到所得产物的结构和重排速率，这些重排显示为分子内。3，还可以直接从d-甘露糖二乙基二硫缩醛制备4-O-异亚丙基-d-甘露糖二乙基二硫缩醛。产物与起始物质的比例一致表明，4,5-反式-二取代的2,2-二甲基-1,3-二氧戊环产物比4-取代的2,2-二甲基-酯稳定约1.2 kcal.mol -1。 1,3-二氧戊环原料。在高浓度和低浓度酸的存在下，d-葡萄糖二乙基二硫缩醛与过量的2-甲氧基丙烯反应，主要得到2
• Zinc mediated deoxygenation of 4-hydroxy-2-butenoic acid moiety. An application for the synthesis of multifunctional chiral synthon
  作者：J.S Yadav、D.K Barma

  DOI：10.1016/0040-4020(96)00093-2

  日期：1996.3

  A facile and practical method for the deoxygenation of 4-alkoxy-2-butenoic acid moiety mediated by zinc is described to prepare multifunctional chiral building blocks from carbohydrates and tartaric acid.

  描述了由锌介导的4-烷氧基-2-丁烯酸部分脱氧的简便实用方法，以由碳水化合物和酒石酸制备多功能手性结构单元。
• Practical synthesis of an enantiomerically pure intermediate of the lactone moiety of mevinic acids
  作者：Serafin Valverde、J. Cristobal Lopez、Ana M. Gomez、Silvestre Garcia-Ochoa

  DOI：10.1021/jo00031a056

  日期：1992.2
• Eine einfache Synthese aller vier stereoisomeren 2,2,5-Trimethyl-1,3-dioxolan-4-carbaldehyde
  作者：W. H. Binder、R. H. Prenner、W. Schmid

  DOI：10.1007/bf01277638

  日期：1994.6

  A simple and efficient procedure for the syntheses of all four stereoisomers of the 2,2,5-trimethyl-1,3-dioxolane-4-carbaldehydes 1a-1d has been developed. Starting with readily available aldopentose diethyl dithioacetals 2, 6, 10 and 14, the title compounds were obtained by a selective protecting group strategy and subsequent Raney-nickel reduction, followed by lead tetraacetate cleavage. This procedure allows an application on a multigram scale.
• Photolysis of 2-azi-2-deoxy-d-arabino-hexitol and analogous hexitols; the ineffectiveness of certain carbohydrate diazirines as photoaffinity labels
  作者：Jochen Lehmann、Stefan Petry

  DOI：10.1016/0008-6215(93)84209-o

  日期：1993.2

  Three diazirines 2-azi-2-deoxy-D-arabino-hexitol (4), its 1-deoxy analogue (5), and 3-azi-3,6-dideoxy-L-xylo-hexitol (9) were synthesised and their products of photolysis analysed by TLC. Diazirine 4 gave exclusively 2-deoxy-D-arabino-hexose (12), 5 gave predominantly 1,2-dideoxy-D-erythro-3-hexulose (10) and 1-deoxy-D-glucitol (11), and 9 did not yield any main product. Carrying out the irradiation of 4 in D2O gave selectively (2S)-2-deoxy-D-arabino-(2-H-2)hexose (12a). The results indicate that photolysis of a diazirine flanked by a hydroxymethyl group, as in compound 4, leads to a rapid and stereoselective intramolecular reaction of the intermediate. This may be an explanation of why compound 4 is ineffective as a photoaffinity reagent for mannitol permease (D-mannitol-specific enzyme II) of the E. coli phosphotransferase system for which it is a substrate. A secondary hydroxymethylene group has a less pronounced effect and still allows some reaction with the medium.