trans-3-nonyloxirane-2-carbaldehyde

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 环氧化物
• 英文名称: trans-3-nonyloxirane-2-carbaldehyde
• 英文别名: (2R,3S)-3-nonyloxirane-2-carbaldehyde
• 化学式: C₁₂H₂₂O₂
• 分子量: 198.305
• InChiKey: WJEHBSHUBXDAJC-RYUDHWBXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  14
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  29.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  trans-3-nonyloxirane-2-carbaldehyde 在 diethylzinc 、 氯化铵 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 24.0h， 生成 (-)-tert-butyl (2R,3S,4R)-2-[(tert-butyldimethylsiloxy)methyl]-4-[(E)-(4S,5S)-epoxytetradec-(1R)-hydroxy-2-en-1-yl]-3-(ethoxydiphenylsilyl)-5-oxopyrrolidine-1-carboxylate
  参考文献：
  名称：

  Fleming−Tamao Oxidation and Masked Hydroxyl Functionality:  Total Synthesis of (+)-Pramanicin and Structural Elucidation of the Antifungal Natural Product (−)-Pramanicin

  摘要：

  The total synthesis of (+)-pramanicin (41b) is reported, thereby establishing the relative and absolute stereochemistry of the naturally occurring antifungal agent. The key steps involve (i) conjugate addition of the diethyl((diethylamino)diphenylsilyl)zincate to a suitably protected gamma-lactam 3 and quenching of the resultant enolate with the alpha,beta-unsaturated gamma,delta-epoxy aldehyde 2 (X = H), (ii) Ni(acac)(2)-catalyzed hydroxylation of a beta-dicarbonyl array, and (iii) Fleming-Tamao oxidation to reveal the masked C-3 hydroxyl group.

  DOI：

  10.1021/jo9905672
• 作为产物：
  描述：

  (2S,3S)-2,3-epoxydodecan-1-ol 在 碳酸氢钠 、 pyridinium chlorochromate 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 生成 trans-3-nonyloxirane-2-carbaldehyde
  参考文献：
  名称：

  (-)-Posticlure 的有效合成：Orgyia postica 的性信息素

  摘要：

  描述了从 L-酒石酸二乙酯中高效合成 (-)-posticlure，这是在 Orgyia postica 中发现的第一种反式环氧化物性信息素。合成分七个步骤完成，总产率为 27%。该合成策略以双维蒂希烯化和二醇立体选择性一锅法转化为环氧化物为关键步骤。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

  DOI：

  10.1002/ejoc.200700449

文献信息

• Mechanistic Insights from Reaction of α-Oxiranyl-Aldehydes with Cyanobacterial Aldehyde Deformylating Oxygenase
  作者：Debasis Das、Benjamin Ellington、Bishwajit Paul、E. Neil G. Marsh

  DOI：10.1021/cb400772q

  日期：2014.2.21

  corresponding oxiranes. Performing the reaction in D2O allowed the facial selectivity of proton addition to be examined by 1H NMR spectroscopy. The proton is delivered with equal probability to either face of the oxirane ring, indicating the formation of an oxiranyl radical intermediate that is free to rotate during the reaction. Unexpectedly, the enzyme also catalyzes a side reaction in which oxiranyl-aldehydes

  源自脂肪酸的长链脂肪烃的生物合成在自然界中广泛存在。该途径的最后一步涉及将脂肪醛脱羰为相应的烷烃或烯烃。在蓝藻中，这是由醛去甲酰加氧酶催化的。我们已经使用与醛碳相邻的带有环氧乙烷环的底物研究了这种酶的机制。该酶催化这些底物的去甲酰化以产生相应的环氧乙烷。在 D 2 O 中进行反应允许通过1检查质子添加的面部选择性核磁共振谱。质子以相等的概率传递到环氧乙烷环的任一面，表明在反应过程中形成了可自由旋转的环氧乙烷自由基中间体。出乎意料的是，该酶还催化了一个副反应，其中环氧乙烷醛进行串联去甲酰化以提供短两个碳的烷烃。我们提供的证据表明，这涉及在第一步中形成的中间体环氧乙烷基的重排，导致在第二步中进一步去甲酰化的醛。这些观察结果为去甲酰化的自由基机制提供了支持，此外，允许基于环氧乙烷基重排的速率常数的先前测量来估计自由基中间体的寿命。
• Posticlure: a novel trans-epoxide as a sex pheromone component of the tussock moth, Orgyia postica (Walker)
  作者：Sadao Wakamura、Norio Arakaki、Masanobu Yamamoto、Syuntaro Hiradate、Hiroe Yasui、Tetsuya Yasuda、Tetsu Ando

  DOI：10.1016/s0040-4039(00)02038-4

  日期：2001.1

  A single EAG-active component was found in a pheromone extract from virgin females of the tussock moth, Orgyia postica. This compound nam ed posticlure possesses a trans-epoxy ring and was identified as (6Z,9Z,11S,12S)-11,12-epoxyhenicosa-6,9-diene by means of GC-MS, H-1 NMR and chiral HPLC analyses, and further chemical derivation followed by the GC-MS analysis. In a field test with. the pheromone synthesized stereoselectively, the male moths were specifically attracted to the (11S,12S)-isomer but not to the antipode. (C) 2001 Elsevier Science Ltd. All rights reserved.
• Fleming−Tamao Oxidation and Masked Hydroxyl Functionality:  Total Synthesis of (+)-Pramanicin and Structural Elucidation of the Antifungal Natural Product (−)-Pramanicin
  作者：Anthony G. M. Barrett、John Head、Marie L. Smith、Nicholas S. Stock、A. J. P. White、D. J. Williams

  DOI：10.1021/jo9905672

  日期：1999.8.1

  The total synthesis of (+)-pramanicin (41b) is reported, thereby establishing the relative and absolute stereochemistry of the naturally occurring antifungal agent. The key steps involve (i) conjugate addition of the diethyl((diethylamino)diphenylsilyl)zincate to a suitably protected gamma-lactam 3 and quenching of the resultant enolate with the alpha,beta-unsaturated gamma,delta-epoxy aldehyde 2 (X = H), (ii) Ni(acac)(2)-catalyzed hydroxylation of a beta-dicarbonyl array, and (iii) Fleming-Tamao oxidation to reveal the masked C-3 hydroxyl group.
• An Efficient Synthesis of (–)-Posticlure: The Sex Pheromone ofOrgyia postica
  作者：Rodney A. Fernandes

  DOI：10.1002/ejoc.200700449

  日期：2007.10

  An efficient multigram synthesis of (–)-posticlure, the first trans-epoxide sex pheromone found in Orgyia postica, from diethyl L-tartrate is described. The synthesis was completed in seven steps and 27 % overall yield. The synthetic strategy features double-Wittig olefination and a stereoselective one-pot conversion of diol to epoxide as the key steps. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim

  描述了从 L-酒石酸二乙酯中高效合成 (-)-posticlure，这是在 Orgyia postica 中发现的第一种反式环氧化物性信息素。合成分七个步骤完成，总产率为 27%。该合成策略以双维蒂希烯化和二醇立体选择性一锅法转化为环氧化物为关键步骤。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)