2-(tetrahydro-6-oxo-2H-pyran-2-yl)-<1α,2β(S)>-cyclopropanecarboxaldehyde | 165038-12-0

• 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: 2-(tetrahydro-6-oxo-2H-pyran-2-yl)-<1α,2β(S)>-cyclopropanecarboxaldehyde
• 英文别名: (1R,2R)-2-((S)-6-oxotetrahydro-2H-pyran-2-yl)cyclopropanecarbaldehyde；(1R,2R)-2-[(2S)-6-oxooxan-2-yl]cyclopropane-1-carbaldehyde
• CAS: 165038-12-0
• 化学式: C₉H₁₂O₃
• 分子量: 168.192
• InChiKey: BJLRZRBGFHEVOW-RNJXMRFFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(tetrahydro-6-oxo-2H-pyran-2-yl)-<1α,2β(S)>-cyclopropanecarboxaldehyde 在 chromium dichloride 、 lithium hydroxide 、 戴斯-马丁氧化剂 、 nickel dichloride 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 21.0h， 生成 (S)-5-[(1R,2R)-2-((2E,6Z)-Dodeca-2,6-dienoyl)-cyclopropyl]-5-hydroxy-pentanoic acid
  参考文献：
  名称：

  Cyclopropane-Containing Eicosanoids of Marine Origin. Biomimetic Synthesis of Constanolactones A and B from the Alga Constantinea simplex

  摘要：

  Asymmetric syntheses of 7, a substance isolated from incubation of arachidonic acid with an acetone powder of the coral Plexaura homomalla, and of constanolactones A (9) and B (10), metabolites of the red alga Constantinea simplex, are described. The key step involves stannic chloride-mediated cyclization of the oxirane derived from Sharpless epoxidation of 10-hydroxy-5,8-decadienoates, and is shown to yield a trans disubstituted cyclopropane Linked to a delta-lactone. Both (R) and (S) configurations at C5 of the lactone are produced in the cyclization, the ratio being independent of olefin geometry in the acyclic precursor, Elaboration of the cyclization products via Nozaki-Kishi coupling of the derived aldehydes 26 and 37 with the appropriate (1E,5Z)-1-iodo-1,5-undecadiene led to 7, 9, and 10, thereby establishing the relative configuration of 7 and confirming the absolute configuration of 9 and 10.

  DOI：

  10.1021/ja00128a008
• 作为产物：
  描述：

  (S)-6-{(1R,2R)-2-[(2,4-Dinitro-phenyl)-hydrazonomethyl]-cyclopropyl}-tetrahydro-pyran-2-one 在 二甲基硫 、 臭氧 作用下， 生成 2-(tetrahydro-6-oxo-2H-pyran-2-yl)-<1α,2β(S)>-cyclopropanecarboxaldehyde
  参考文献：
  名称：

  Cyclopropane-Containing Eicosanoids of Marine Origin. Biomimetic Synthesis of Constanolactones A and B from the Alga Constantinea simplex

  摘要：

  Asymmetric syntheses of 7, a substance isolated from incubation of arachidonic acid with an acetone powder of the coral Plexaura homomalla, and of constanolactones A (9) and B (10), metabolites of the red alga Constantinea simplex, are described. The key step involves stannic chloride-mediated cyclization of the oxirane derived from Sharpless epoxidation of 10-hydroxy-5,8-decadienoates, and is shown to yield a trans disubstituted cyclopropane Linked to a delta-lactone. Both (R) and (S) configurations at C5 of the lactone are produced in the cyclization, the ratio being independent of olefin geometry in the acyclic precursor, Elaboration of the cyclization products via Nozaki-Kishi coupling of the derived aldehydes 26 and 37 with the appropriate (1E,5Z)-1-iodo-1,5-undecadiene led to 7, 9, and 10, thereby establishing the relative configuration of 7 and confirming the absolute configuration of 9 and 10.

  DOI：

  10.1021/ja00128a008

文献信息

• Enantioselective Total Synthesis of Eicosanoid and Its Congener, Using Organocatalytic Cyclopropanation, and Catalytic Asymmetric Transfer Hydrogenation Reactions as Key Steps
  作者：Gullapalli Kumaraswamy、Mogilisetti Padmaja

  DOI：10.1021/jo800631z

  日期：2008.7.1

  An enantioselective unified strategy for the syntheses of the oxylipin class of natural products was accomplished. Our strategy relies on three catalytic steps: (a) organocatalytic cyclopropanation, (b) the catalytic asymmetric transfer hydrogenation (CATHy) reaction, and (c) the Nozaki-Hiyama-Kishi reaction.
• Cyclopropane-Containing Eicosanoids of Marine Origin. Biomimetic Synthesis of Constanolactones A and B from the Alga Constantinea simplex
  作者：James D. White、Mark S. Jensen

  DOI：10.1021/ja00128a008

  日期：1995.6

  Asymmetric syntheses of 7, a substance isolated from incubation of arachidonic acid with an acetone powder of the coral Plexaura homomalla, and of constanolactones A (9) and B (10), metabolites of the red alga Constantinea simplex, are described. The key step involves stannic chloride-mediated cyclization of the oxirane derived from Sharpless epoxidation of 10-hydroxy-5,8-decadienoates, and is shown to yield a trans disubstituted cyclopropane Linked to a delta-lactone. Both (R) and (S) configurations at C5 of the lactone are produced in the cyclization, the ratio being independent of olefin geometry in the acyclic precursor, Elaboration of the cyclization products via Nozaki-Kishi coupling of the derived aldehydes 26 and 37 with the appropriate (1E,5Z)-1-iodo-1,5-undecadiene led to 7, 9, and 10, thereby establishing the relative configuration of 7 and confirming the absolute configuration of 9 and 10.