2-C-hydroxymethyl-2,3-O-isopropylidene-D-erythrofuranose | 396092-68-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-C-hydroxymethyl-2,3-O-isopropylidene-D-erythrofuranose
• 英文别名: (3aR,6aR)-3a-(hydroxymethyl)-2,2-dimethyl-6,6a-dihydro-4H-furo[3,4-d][1,3]dioxol-4-ol
• CAS: 396092-68-5
• 化学式: C₈H₁₄O₅
• 分子量: 190.196
• InChiKey: YRCUKVHLSFCSAS-ONHAXZMJSA-N

物化性质

• 沸点：
  327.1±42.0 °C(Predicted)
• 密度：
  1.313±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.7
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  68.2
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2-C-hydroxymethyl-2,3-O-isopropylidene-D-erythrofuranose 在 盐酸 、 氢氧化钾 、 硫酸 作用下， 以 乙醚 、 丙酮 为溶剂， 反应 87.0h， 生成 2-C-(benzyloxymethyl)-D-erythrose
  参考文献：
  名称：

  1-Deoxy-d-xylulose:  Synthesis Based on Molybdate-Catalyzed Rearrangement of a Branched-Chain Aldotetrose

  摘要：

  [GRAPHICS]1-Deoxy-D-xylulose has been prepared in seven steps and similar to 21% overall yield from 2,3-O-isopropylidene-D-erythrono-1,4-lactone. The key reaction involves transformation of a branched-chain aldotetrose to the 1-deoxy-2-ketopentose catalyzed by molybdic acid. Other branched-chain aldotetroses containing bulkier substituents at C2 also engage in the conversion, suggesting routes to protected 2-ketoses and alpha -ketoacids/ esters. This synthetic route mimics reactions of the non-mevalonate isoprenoid pathway in plants and bacteria.

  DOI：

  10.1021/ol016265f
• 作为产物：
  描述：

  D-erythronolactone acetonide 在 sodium tetrahydroborate 、 potassium carbonate 作用下， 以 甲醇 、 水 为溶剂， 反应 49.5h， 生成 2-C-hydroxymethyl-2,3-O-isopropylidene-D-erythrofuranose
  参考文献：
  名称：

  1-Deoxy-d-xylulose:  Synthesis Based on Molybdate-Catalyzed Rearrangement of a Branched-Chain Aldotetrose

  摘要：

  [GRAPHICS]1-Deoxy-D-xylulose has been prepared in seven steps and similar to 21% overall yield from 2,3-O-isopropylidene-D-erythrono-1,4-lactone. The key reaction involves transformation of a branched-chain aldotetrose to the 1-deoxy-2-ketopentose catalyzed by molybdic acid. Other branched-chain aldotetroses containing bulkier substituents at C2 also engage in the conversion, suggesting routes to protected 2-ketoses and alpha -ketoacids/ esters. This synthetic route mimics reactions of the non-mevalonate isoprenoid pathway in plants and bacteria.

  DOI：

  10.1021/ol016265f

文献信息

• Synthesis and cytotoxic evaluation of novel pyrimidine deoxyapiothionucleosides
  作者：Stefanos S. Kotoulas、Vesna V. Kojić、Gordana M. Bogdanović、Alexandros E. Koumbis

  DOI：10.1016/j.bmcl.2013.03.091

  日期：2013.6

  realized following application of a versatile and high-yielding scheme, which utilized inexpensive l- and d-arabinose as starting materials, respectively, and which makes use of a regio- and stereo-selective Pummerer rearrangement reaction for the coupling of the nucleobase with the thiosugar moiety. Some of the targeted compounds have shown selective cytotoxic effects (with IC50 <10 μM) against specific

  d-和l-系列的新型嘧啶脱氧硫代硫代核苷的合成是通过应用一种通用且高产的方案实现的，该方案分别利用廉价的l-和d-阿拉伯糖作为起始原料，并利用区域和氨基酸。立体选择性Pummerer重排反应，用于将核碱基与硫糖部分偶联。一些目标化合物已显示出 对特定癌细胞系的选择性细胞毒作用（IC 50 <10μM）。所有测试的化合物对测试的正常细胞系均无细胞毒性作用。
• d- and l-Erythrose as sources of chiral quaternary carbon centers. Total synthesis of (−)-malyngolide and (+)-tanikolide
  作者：Alexandros E. Koumbis、Kyriaki M. Dieti、Myrofora G. Vikentiou、John K. Gallos

  DOI：10.1016/s0040-4039(03)00290-9

  日期：2003.3

  A highly efficient and versatile approach was applied for the total synthesis of the marine natural products (−)-malyngolide and (+)-tanikolide from isopropylidene l- and d-erythrose, using a common strategy.

  使用一种通用策略，将高效，通用的方法用于从异亚丙基l-和d-赤藓糖中全合成海洋天然产物（-）-麦芽糖内酯和（+）-tanikolide。
• A convenient synthesis of 2-C-methyl-d-erythritol 4-phosphate and isotopomers of its precursor
  作者：Alexandros E. Koumbis、Stefanos S. Kotoulas、John K. Gallos

  DOI：10.1016/j.tet.2006.12.078

  日期：2007.3

  A new synthetic approach toward 2-C-methyl-d-erythritol 4-phosphate (MEP), a key intermediate in the mevalonate-independent biosynthetic pathway for isoprenoids, and deuterated analogues of its precursor, 2-C-methyl-d-erythritol acetonide, is described. This procedure uses 2-C-methyl-d-erythrose acetonide as starting material and delivers, through a mono-protection strategy, the target compounds in

  一种新的合成方法，用于合成2 - C-甲基-d-赤藓糖醇4-磷酸酯（MEP），它是类异戊二烯的甲羟戊酸非依赖型生物合成途径的关键中间体，及其前体2 - C-甲基-d-赤藓糖醇的氘代类似物描述了乙炔化物。该方法使用2 - C-甲基-d-赤藓糖丙酮化物为起始原料，并通过单保护策略以短方式且高收率递送目标化合物。
• Carbon-branched carbohydrate chirons: synthesis of C-3 and C-4-branched sugar lactones derived from d-erythronolactone
  作者：Sarah F. Jenkinson、K. Victoria Booth、Amalia M. Estévez Reino、Graeme Horne、Ramón J. Estévez、George W.J. Fleet

  DOI：10.1016/j.tetasy.2009.08.029

  日期：2009.10

  Two carbon chain extensions using a Wittig reaction on both a 1-deoxy ribulose derivative and a C-2-branched erythrose derivative are reported. Subsequent dihydroxylation resulted in the synthesis of C-3 and C-4 methyl-branched sugar lactones, the useful synthetic building blocks. Control of the stereoselectivity of both the Wittig reaction and the dihydroxylation is investigated, and 3-C-methyl and

  报道了使用Wittig反应在1-脱氧核糖衍生物和C-2-支化赤藓糖衍生物上的两个碳链延伸。随后的二羟基化作用导致合成了C-3和C-4甲基支链糖内酯，它们是有用的合成构件。研究了Wittig反应和二羟基化反应的立体选择性的控制，并研究了3- C-甲基和4- C-甲基d-altrono-1,4-内酯和d-glucono-1,4-内酯和4- C合成了-羟甲基-d-altrono-1,4-内酯。
• Synthesis of Carbohydrates in Mineral-Guided Prebiotic Cycles
  作者：Hyo-Joong Kim、Alonso Ricardo、Heshan I. Illangkoon、Myong Jung Kim、Matthew A. Carrigan、Fabianne Frye、Steven A. Benner

  DOI：10.1021/ja201769f

  日期：2011.6.22

  One present obstacle to the "RNA-first" model for the origin of life is an inability to generate reasonable "hands off" scenarios for the formation of carbohydrates under conditions where they might have survived for reasonable times once formed. Such scenarios would be especially compelling if they deliver pent(ul)oses, five-carbon sugars found in terran genetics, and exclude other carbohydrates (e.g., aldotetroses) that may also be able to function in genetic systems. Here, we provide detailed chemical analyses of carbohydrate premetabolisin, showing how borate, molybdate, and calcium minerals guide the formation of tetroses (C(4)H(8)O(4)), heptoses (C(7)H(14),O(7)), and pentoses (C(5)H(10)O(5)), including the ribose found in RNA, in "hands off" experiments, starting with formaldehyde and glycoaldehyde. These results show that pent(ul)oses would almost certainly have formed as stable borate complexes on the surface of an early Earth beneath a humid CO(2) atmosphere suffering electrical discharge. While aldotetroses form extremely stable complexes with borate, they are not accessible by pathways plausible under the most likely early Earth scenarios. The stabilization by borate is not, however, absolute. Over longer times, material is expected to have passed from borate-bound pent(ul)oses to a branched heptulose, which is susceptible to Cannizzaro reduction to give dead end products. We show how this fate might be avoided using molybdate-catalyzed rearrangement of a branched pentose that is central to borate-moderated cycles that fix carbon from formaldehyde. Our emerging understanding of the nature of the early Earth, including the presence of hydrated rocks undergoing subduction to form felsic magmas in the early Hadean eon, may have made borate and molydate species available to prebiotic chemistry, despite the overall "reduced" state of the planet.