(2S,4S,5R)-5-羟基-2-甲基-1,3-二恶烷-4-甲醛 | 87068-62-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二恶烷
• 中文名称: (2S,4S,5R)-5-羟基-2-甲基-1,3-二恶烷-4-甲醛
• 英文名称: 2,4-O-(1S)-ethylidene-D-threose
• 英文别名: 2,4-O-(S)-ethylidene-D-threose；2,4-O-ethylidene-D-threose；1,3-Dioxane-4-carboxaldehyde, 5-hydroxy-2-methyl-, (2S,4S,5R)-；(2S,4S,5R)-5-hydroxy-2-methyl-1,3-dioxane-4-carbaldehyde
• CAS: 87068-62-0
• 化学式: C₆H₁₀O₄
• 分子量: 146.143
• InChiKey: HVAFLFRNUVFTBL-KVQBGUIXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.3
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2S,4S,5R)-5-羟基-2-甲基-1,3-二恶烷-4-甲醛 在 palladium on activated charcoal 盐酸 、 氢气 、 4-甲基苯磺酸吡啶 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 19.0h， 生成 (2S,4R,5R,E)-5-hydroxy-4-((3-methyl-2-pentenoic acid ethyl ester)-5-yl)-2-methyl-1,3-dioxane
  参考文献：
  名称：

  Radical-Mediated Construction of Cyclopentane with Concurrent Formation of a Well-Defined Quaternary Center

  摘要：

  Synthetic efforts toward the total synthesis of clavulactone dealing with enantioselective construction of the cyclopentane moiety are reported. With a novel radical-mediated cyclization as key step, the current approach allows for concurrent enantioselective construction of a quaternary chiral carbon at the cyclization step. The stereochemistries of the newly formed chiral centers are dictated by the configuration of the C-1 (cf. numbering in 1). The high selectivity observed in this work is ascribed to the conformational advantage of the cyclic acetal, which results in a much better defined transition state than the previously used open-chain counterpart does.

  DOI：

  10.1021/jo9822380

文献信息

• 1,3-Dipolar Cycloadditions of D-Erythrose- and D-Threose-Derived Alkenes with Nitrones
  作者：Iva Blanáriková-Hlobilová、Lubor Fišera、Naďa Prónayová、Marian Koman

  DOI：10.1135/cccc20030951

  日期：——

  The new chiral terminal alkenes derived from cyclic acetals of D-erythrose 1-3 and D-threose 5, 6 were prepared. The alkenes 1, 2 and 5 react with chiral nitrones to afford the corresponding diastereomeric isoxazolidines 19-21. The stereoselectivity was dependent on the steric hindrance of the nitrone. In all cases the cycloadditions are endo-selective. The major products were found to have the C-3/C-4 erythro- and C-3/C-3a cis-configuration. Its formation can be rationalized by a less hindered endo-attack of the (Z)-nitrone in an antiperiplanar manner with respect to the largest group of the cyclic acetal.

  新的手性末端烯烃是从D-赤糖醛的环丙醛缩酮1-3和D-甘露醛5，6制备的。烯烃1，2和5与手性亚胺反应，得到相应的二对映异构异氧杂环己烷19-21。立体选择性取决于亚胺的立体位阻。在所有情况下，环加成反应都是内向选择性的。主要产物发现具有C-3/C-4 erythro-和C-3/C-3a cis-构型。其形成可以通过较少位阻的(Z)-亚胺以与环丙醛最大基团相对于反平面方式的内向进攻来解释。
• Synthesis of D-erythrose and D-threose derived nitrones and cycloadditions to styrene
  作者：Juraj Kubáň、Iva Blanáriková、L'ubor Fišera、Libuše Jarošková、Marion Fengler-Veith、Volker Jäger、Jozef Kožíšek、Otakar Humpa、Nad'a Prónayová、Vratislav Langer

  DOI：10.1016/s0040-4020(99)00512-8

  日期：1999.7

  The new nitrones derived from cyclic acetals of D-erythrose (2a-c) and D-threose (8) react with styrene to afford the corresponding 3,5-disubstituted diastereomeric isoxazolidines 3–6 and 9–12. The stereoselectivity was dependent on the steric hindrance of the nitrone. The major products 3a-c (55–58 %) and 9 (73 %) were found to have the C-3/C-4′ erythro and C-3/C-5 cis relative configuration by X-ray

  衍生自D-赤藓糖（2a-c）和D-苏糖（8）的环状缩醛的新硝酮与苯乙烯反应，生成相应的3,5-二取代的非对映异构异恶唑烷3-6和9-12。立体选择性取决于硝酮的空间位阻。通过X射线分析发现主要产物3a-c（55-58％）和9（73％）具有C-3 / C-4'赤型和C-3 / C-5顺式相对构型。相对于最大的环状缩醛基团，可以通过以反平面方式较少地阻碍Z-硝基的内攻击来合理化其形成。
• Studies toward the Total Synthesis of Clavulactone
  作者：Qiang Zhu、Lixin Qiao、Yikang Wu、Yu-Lin Wu

  DOI：10.1021/jo005683f

  日期：2001.4.1

  Synthetic studies directed toward a total synthesis of clavulactone are reported. In light of the analysis made in our previous work, cyclopentane 4a (a key intermediate in the present work) was synthesized through a radical-mediated ring closure of a rationally designed substrate 25. Using HWE reactions, the lower and upper side-chains of 4a were converted into an allyl chloride and an allyl cyanohydrin

  已经报道了针对克拉维内酯的总合成的合成研究。根据我们先前的工作进行的分析，通过合理设计的底物25的自由基介导的闭环合成了环戊烷4a（当前工作的关键中间体）。使用HWE反应，将4a分别转化为烯丙基氯和烯丙基氰醇。随后用双（三甲基甲硅烷基）酰胺钠在高度稀释的THF溶液中处理烯丙基氯/氰醇，导致分子内烷基化，从而完成了合成多烯丙基骨架，十一元环的构建的主要工作。还描述了SmI（2）介导的内酯化反应，作为形成克拉维内酯的α，β-不饱和δ-内酯片段的模型反应。
• Synthetic study on chiral building block of vicinal diol, chiron approach to the precursors of all sphingosine stereoisomers
  作者：Yun-Long Li、Xiao-Ling Sun、Yu-Lin Wu

  DOI：10.1016/s0040-4020(01)89265-6

  日期：1994.1

  All enantiomeric stereoisomers of 1,2,3-trihydroxy-4E-octadecene, key intermediates for the syntheses of sphingosines, were prepared using sugar as chiral pool
• Li, Yun-Long; Mao, Xiu-Hong; Wu, Yu-Lin, Journal of the Chemical Society. Perkin transactions I, 1995, # 12, p. 1559 - 1564
  作者：Li, Yun-Long、Mao, Xiu-Hong、Wu, Yu-Lin

  DOI：——

  日期：——