(+/-)-4-exo-hydroxy-2-oxabicyclo[3.3.0]oct-7-en-3-one

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (+/-)-4-exo-hydroxy-2-oxabicyclo[3.3.0]oct-7-en-3-one
• 英文别名: 3a,4-dihydro-3-hydroxy-3H-cyclopenta[b]furan-2(6aH)-one；(3R,3aR,6aR)-3-hydroxy-3,3a,4,6a-tetrahydro-2H-cyclopenta[b]furan-2-one；3-hydroxy-3,3a,4,6a-tetrahydro-cyclopenta[b]furan-2-one；Rel-(3R,3aR,6aR)-3-hydroxy-3,3a,4,6a-tetrahydro-2H-cyclopenta[b]furan-2-one；(3R,3aR,6aR)-3-hydroxy-3,3a,4,6a-tetrahydrocyclopenta[b]furan-2-one
• 化学式: C₇H₈O₃
• 分子量: 140.139
• InChiKey: LOTRXPYWDQSASJ-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：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (+/-)-4-exo-hydroxy-2-oxabicyclo[3.3.0]oct-7-en-3-one 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以93%的产率得到(1R*,5S*)-5-[(1R*)-1,2-dihydroxyethyl]-cyclopent-2-en-1-ol
  参考文献：
  名称：

  A Facile Synthesis of cis-9-[4-(1,2-Dihydroxyethyl)-cyclopent-2-enyl]guanine and Its Derivative

  摘要：

  The synthesis of carbocyclic nucleosides, cis-9-[4-(1,2-dihydroxyethyl)-cyclopent-2-enyl]guanine (3) and cis-2-amino-6-cyclopropylamino-9-[4-(1,2-dihydroxyethyl)-cyclopent-2- enyl]purine (4), was achieved from cyclopentadiene (5) in five and six steps, respectively. This route involves a hetero Diels-Alder reaction and a Pd(0)-catalyzed coupling reaction.

  DOI：

  10.1080/15257770008035034
• 作为产物：
  描述：

  环戊二烯 、 乙醛酸 在 bismuth(lll) trifluoromethanesulfonate 、 水 作用下， 反应 2.0h， 生成 (3S,3aR,6aR)-3a,4-dihydro-3-hydroxy-3H-cyclopenta[b]furan-2(6aH)-one 、 (+/-)-4-exo-hydroxy-2-oxabicyclo[3.3.0]oct-7-en-3-one
  参考文献：
  名称：

  Enhancement of Dienophilic and Enophilic Reactivity of the Glyoxylic Acid by Bismuth(III) Triflate in the Presence of Water

  摘要：

  三氟甲烷磺酸铋(III)（1）在水的存在下，能够高效催化羟基乙酸与经典二烯或取代烯烃之间的羰基-达尔斯-阿尔德反应或羰基-烯反应。

  DOI：

  10.1055/s-1998-1869

文献信息

• Conversion of (–)-4-hydroxy-2-oxabicyclo[3.3.0]oct-7-en-3-one into the anti-HIV agent carbovir
  作者：Rosemary A. MacKeith、Ray McCague、Horacio F. Olivo、Christopher F. Palmer、Stanley M. Roberts

  DOI：10.1039/p19930000313

  日期：——

  The lactone (±)-1 was resolved using Pseudomonas fluorescens lipase and vinyl acetate; the ester (–)-3 obtained by this process was subsequently converted into the anti-HIV agent carbovir (–)-9.

  使用荧光假单胞菌脂肪酶和乙酸乙烯酯拆分内酯（±）-1。随后将通过此方法获得的酯（–）- 3转化为抗HIV药剂carbovir（–）- 9。
• Formation of bromohydrins and epoxides from 4-hydroxy-2-oxabicyclo[3.3.0]oct-7-en-3-one and 9-hydroxy-7-oxabicyclo[4.3.0] non-4-en-8-one
  作者：Antonio Garofalo、Michael B. Hursthouse、K. M. Abdul Malik、Horacio F. Olivo、Stanley M. Roberts、Vladimir Sik

  DOI：10.1039/p19940001311

  日期：——

  The hydroxy lactone 1 and the silylated derivative 8 react selectively with HOBr to give access to polyfunctional bicyclic systems such as the bromo ester 10. The lactone 3 or the corresponding derivative 20 react less selectively to give mixtures of compounds 16, 17, 18, 19, 21, 22. The hydroxybicyclo[4.3.0]nonenones 2 and 4 behave in a similar fashion to the lactone 3, reacting non-selectively with

  羟基内酯1和甲硅烷基化衍生物8与HOBr选择性反应，可进入多官能双环系统，如溴酸酯10。内酯3或相应的衍生物20反应更少选择性，得到的化合物的混合物16，17，18，19，21，22。羟基双环[4.3.0]壬烯酮2和4的行为与内酯3相似，与HOBr和m发生非选择性反应氯过苯甲酸，以产生化合物双环取代的高度过多23 - 31，33 - 39，41和42。对于四种化合物，二乙酸酯25和37以及环氧化物26和27，获得了X射线晶体结构。
• Kinetic Resolution of Racemic 2-Hydroxy-γ-butyrolactones by Asymmetric Esterification Using Diphenylacetic Acid with Pivalic Anhydride and a Chiral Acyl-Transfer Catalyst
  作者：Kenya Nakata、Kouya Gotoh、Keisuke Ono、Kengo Futami、Isamu Shiina

  DOI：10.1021/ol303453j

  日期：2013.3.15

  Various optically active 2-hydroxy-γ-butyrolactone derivatives are produced via the kinetic resolution of racemic 2-hydroxy-γ-butyrolactones with diphenylacetic acid using pivalic anhydride and (R)-benzotetramisole ((R)-BTM), a chiral acyl-transfer catalyst. Importantly, the substrate scope of this novel protocol is fairly broad (12 examples, s-value; up to over 1000). In addition, we succeeded in

  使用新戊酸酐和（R）-苯并四咪唑（（R）-BTM），手性酰基-转移催化剂。重要的是，该新颖方案的底物范围相当广泛（12个例子，s值；最大超过1000）。此外，我们通过理论计算成功地揭示了提供高对映选择性的反应机理，并阐述了2-羟基内酯在C-3位置的取代基效应。
• Total Synthesis of Prostratin, a Bioactive Tigliane Diterpenoid: Access to Multi-Stereocenter Cyclohexanes from a Phenol
  作者：Guanghu Tong、Zhengwei Ding、Zhi Liu、You-Song Ding、Liang Xu、Hailong Zhang、Pengfei Li

  DOI：10.1021/acs.joc.0c00022

  日期：2020.4.3

  Tiglianes such as prostratin and related diterpenoids are biologically significant natural molecules and long-standing targets for organic synthesis community. Due to the complex polycyclic scaffolds, high oxygenation level, and dense functional groups and stereocenters, their de novo chemical syntheses still face formidable challenges despite extensive efforts in the past 40 years. This account details

  Tiglianes（例如前驱素和相关的二萜类化合物）是生物学上重要的天然分子，也是有机合成社区的长期目标。由于复杂的多环支架，高氧化水平以及密集的官能团和立体中心，尽管在过去的40年中付出了巨大的努力，它们的从头化学合成仍然面临着严峻的挑战。该报告详细介绍了模块化和简明的prostratin（一种有效的抗HIV和抗癌药）合成方法的开发。该合成中的关键方法涉及一系列的氧化脱芳香化作用和外围基团的顺序立体选择性安装，以快速构建连续取代的环己烷C环。在温德（Wender）的工作启发下，开发了一种由酸和溶剂控制的立体发散型环丙烷D环。通过计算方法进行的机理研究表明，分子内和分子间氢键之间的竞争导致不同的构象，因此有利于不同的质子化过程。这项运动中设计和出乎意料的化学反应反映了天然结构的独特性，应该适合未来有关复杂多环分子的化学合成。
• A route to enantiomerically pure 5-(2′-hydroxyethyl)cyclopent-2-en-1-ol and its absolute configuration by Mosher esters
  作者：Hao Chen、Srinivas Nagabandi、Steven Smith、Jonathan M. Goodman、Erika Plettner

  DOI：10.1016/j.tetasy.2009.02.007

  日期：2009.3

  The (+/-)-5-(2'-hydroxyethyl)cyclopent-2-en-1-ol 1 was prepared in a one-pot procedure, and was resolved using lipase AK and vinyl acetate with high ee. This provides a readily available chiral synthon for the synthesis of a wide variety of biologically interesting molecules. Further, the absolute configuration of diol 1 was confirmed directly by the Mosher ester method. (c) 2009 Elsevier Ltd. All rights reserved.