(+)-(1R,4S)-dimethyl (4-hydroxy-2-cyclopenten-1-yl)malonate | 120052-50-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (+)-(1R,4S)-dimethyl (4-hydroxy-2-cyclopenten-1-yl)malonate
• 英文别名: 2-(4-hydroxy-cyclopent-2-enyl)-malonic acid dimethyl ester；dimethyl [(1R,4S)-4-hydroxycyclopent-2-enyl]malonate；dimethyl (1-hydroxycyclopent-2-en-4-yl)malonate；2-<(1R,4S)-4-hydroxycyclopent-2-enyl>malonsaeure-dimethylester；dimethyl 2-[(1R,4S)-4-hydroxycyclopent-2-en-1-yl]propanedioate
• CAS: 120052-50-8
• 化学式: C₁₀H₁₄O₅
• 分子量: 214.218
• InChiKey: PWSYHNSLZSFQKV-NKWVEPMBSA-N

物化性质

• 沸点：
  294.3±25.0 °C(Predicted)
• 密度：
  1.252±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  72.8
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (+)-(1R,4S)-dimethyl (4-hydroxy-2-cyclopenten-1-yl)malonate 在 potassium iodide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 2-((1s,4s)-4-羟基-2-环戊烯基)乙酸甲酯
  参考文献：
  名称：

  Δ的高效全合成12 -PGJ 2，15-脱氧Δ 12,14 -PGJ 2，和它们的类似物

  摘要：

  4-环戊烯-1,3-二醇单乙酸酯（> 95％ee）的TBS醚与衍生自丙二酸甲酯的阴离子和t- BuOK和LDA等碱的钯催化反应进行得非常高效且可重复。以> 90％的分离产率获得的产物经五步转化为在γ位具有α链的关键环戊烯酮。该烯酮与ω-链醛的醛醇缩合反应得到醛醇加合物，并且将衍生的甲磺酸酯暴露于Al 2 O 3提供了完整结构的交联二烯酮。最后，官能团操作布置Δ 12 -PGJ 2有效。同样，15-脱氧Δ 12,14 -PGJ 2合成了5，6-乙炔类似物和5，6-二氢类似物。

  DOI：

  10.1016/j.tet.2006.01.051
• 作为产物：
  描述：

  顺式-4-(苯甲酰氧基)-2-环戊烯基苯甲酸酯 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 magnesium methanolate 、 [(1R,2R)-N-(2-aminocyclohexyl)]-2-(diphenylphosphanyl)benzamide 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 28.0h， 生成 (+)-(1R,4S)-dimethyl (4-hydroxy-2-cyclopenten-1-yl)malonate
  参考文献：
  名称：

  A modular approach for ligand design for asymmetric allylic alkylations via enantioselective palladium-catalyzed ionizations

  摘要：

  A new class of ligands for asymmetric transition metal catalysis based on 2-(diphenylphosphino)benzoic acid was used in a mechanistically-defined palladium-catalyzed reaction in which enantiodifferentiation was the result of selective ionization of substrates derived from cis-2-cycloalkene-1,4-diols. By making rational, stepwise changes in the ligand structure, the structural requirements for good asymmetric induction were probed. The absolute stereochemistry of the products was found to be related to the chirality of the ligand in a predictable fashion. A mnemonic is given which allows one to predict the mode of ionization (R or S) solely on the basis of the stereochemistry of the variable chiral linker used to make the ligand.

  DOI：

  10.1021/ja00050a013

文献信息

• Total synthesis of Δ12-PGJ2, 15-deoxy-Δ12,14-PGJ2, and related compounds
  作者：Hukum P. Acharya、Yuichi Kobayashi

  DOI：10.1016/j.tetlet.2003.11.143

  日期：2004.2

  α′-position with the ω-chain aldehydes followed by dehydration to produce the title compounds. In a similar manner, 5-dehydro compounds (acetylene analogues) were synthesized successfully. In addition, palladium-catalyzed reaction of 4-cyclopentene-1,3-diol monoacetate with methyl malonate, the first step of the synthesis, was improved to afford the product in high yield by using t-BuOK or LDA in place

  具有α链的关键环戊烯酮，从4-环戊烯-1,3-二醇单乙酸酯的TBS醚合成，并且在提交给醛醇缩合反应的α '位上与ω-链醛，然后脱水，产生标题化合物。以类似的方式，成功地合成了5-脱氢化合物（乙炔类似物）。另外，通过使用t- BuOK或LDA代替NaH ，改进了合成的第一步钯-催化的4-环戊烯-1，3-二醇单乙酸酯与丙二酸甲酯的反应，从而以高收率提供了产物。
• Enantioselective Synthesis of Both Enantiomers of Dimethyl<i>cis</i>-(4-Acetoxycyclopent-2-enyl)malonate, Key Intermediates for Epijasmonate
  作者：Shinji TANIMORI、Yuko TSUJI、Mitsunori KIRIHATA

  DOI：10.1271/bbb.66.660

  日期：2002.1

  Both enantiomers (3 and 4) of dimethyl cis-(4-acetoxycyclopent-2-enyl)malonate (3), known intermediates for the synthesis of epijasmonate, were prepared in an enantio-enriched form from common starting material 2 based on desymmetrization of the meso-character by palladium-catalyzed asymmetric allylic alkylation.

  顺式-（4-乙酰氧基环戊-2-烯基）丙二酸二甲酯（3）的两种对映异构体（3和4），是合成表茉莉酸酯的已知中间体，是基于对苯二甲酰胺的去对称作用，由常见的起始原料2以对映体富集的形式制备的。钯催化的不对称烯丙基烷基化反应的介观特征。
• Methyl-jasmonat: Ein kurzer Weg zum Naturstoff und seinem unnatürlichen Enantiomer<i>via</i>Palladium(0)-induzierte, enantiodivergente Alkylierung von Cyclopent-2-en-1,3-diol-Derivaten
  作者：Franz-Peter Montforts、Ingrid Gesing-Zibulak、Wassilios Grammenos、Manfred Schneider、Kurt Laumen

  DOI：10.1002/hlca.19890720822

  日期：1989.12.13

  Methyl Jasmonate: A Short Synthesis of Naturally Occurring Methyl Jasmonate and its Unnatural Enantiomer via Enantiodivergent Alkylation of Cyclopent-2-ene-1,3-diol Derivatives by Palladium(0)-Induced Reactions

  茉莉酸甲酯：天然存在的茉莉酸甲酯和其非天然映异构体A短合成通过由钯环戊-2-烯-1,3-二醇衍生物的烷基化Enantiodivergent（0）诱导的反应
• Strategy for synthesis of the isoleucine conjugate of epi-jasmonic acid
  作者：Narihito Ogawa、Yuichi Kobayashi

  DOI：10.1016/j.tetlet.2008.09.144

  日期：2008.12

  The TES ether of 2-((1R,2S,3R)-3-hydroxy-2-((Z)-pent-2-enyl)cyclopentyl)acetic acid (5, equal to the reduction product of epi-jasmonic acid) derived from (1R,4S)-4-hydroxycyclopent-2-enyl acetate (19) in 13 steps was activated by using isobutyl chloroformate and was subjected to condensation with isoleucine at room temperature for 48 h. The product was desilylated and oxidized to the isoleucine conjugate of epi-jasmonic acid in 68% yield over three steps. Similarly, allo-isoleucine conjugate of epi-jasmonic acid and three isoleucine conjugates of ent-epi-jasmonic acid, jasmonic acid, and ent-jasmonic acid were synthesized. (C) 2008 Elsevier Ltd. All rights reserved.
• Enantioselective preparation of functionalized cyclopentanoids via a common chiral (.pi.-allyl)palladium complex
  作者：Donald R. Deardorff、Robert G. Linde、Amanda M. Martin、Michael J. Shulman

  DOI：10.1021/jo00272a059

  日期：1989.5