trans α,β-epoxyhexanal

• 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 α,β-epoxyhexanal
• 英文别名: (2S*,3R*)-2,3-epoxyhexanal；trans-3-propyloxirane-2-carbaldehyde；(2SR,3RS)-2,3-epoxyhexanal；(2R,3S)-3-propyloxirane-2-carbaldehyde
• 化学式: C₆H₁₀O₂
• 分子量: 114.144
• InChiKey: JHKVGIOBTDDGMJ-WDSKDSINSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  8
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 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 α,β-epoxyhexanal 在 molecular sieve 作用下， 以 四氢呋喃 、 二氯甲烷 、 二丁醚 为溶剂， 反应 16.0h， 生成
  参考文献：
  名称：

  Diastereoselective One-Step Synthesis of Functionalized cis-Aziridinyl Alcohols from Oxiranyl Carbaldimines

  摘要：

  Upon treatment with lithiumorganic nucleophiles, trans-configured oxiranyl carbaldimines are transformed into anti-configured cis-aziridinyl alcohols with excellent diastereoselectivity. This conversion may be explained by a new type of the aza-Payne rearrangement, including first a nucleophilic attack on the imine carbon atom with diastereofacial differentiation followed by an intramolecular nucleophilic opening of the oxiranyl ring with simultaneous formation of the aziridine ring.

  DOI：

  10.1021/ol051090l
• 作为产物：
  描述：

  2-已烯醛 在 双氧水 、 potassium hydrogencarbonate 作用下， 以 水 为溶剂， 以30%的产率得到trans α,β-epoxyhexanal
  参考文献：
  名称：

  Diastereoselective One-Step Synthesis of Functionalized cis-Aziridinyl Alcohols from Oxiranyl Carbaldimines

  摘要：

  Upon treatment with lithiumorganic nucleophiles, trans-configured oxiranyl carbaldimines are transformed into anti-configured cis-aziridinyl alcohols with excellent diastereoselectivity. This conversion may be explained by a new type of the aza-Payne rearrangement, including first a nucleophilic attack on the imine carbon atom with diastereofacial differentiation followed by an intramolecular nucleophilic opening of the oxiranyl ring with simultaneous formation of the aziridine ring.

  DOI：

  10.1021/ol051090l

文献信息

• Asymmetric Epoxidation of α,β-Unsaturated Aldehydes in Aqueous Media Catalyzed by Resin-Supported Peptide- Containing Unnatural Amino Acids
  作者：Kengo Akagawa、Kazuaki Kudo

  DOI：10.1002/adsc.201000805

  日期：2011.4.18

  The enantio‐ and diastereoselective epoxidation of α,β‐unsaturated aldehydes in aqueous media was realized using a resin‐supported peptide catalyst. Introducing the hydrophobic and bulky unnatural amino acid 3‐(1‐pyrenyl)alanine into the peptide sequence was effective for enhancing the reaction rate and enantioselectivity.

  使用树脂负载的肽催化剂可实现水性介质中α，β-不饱和醛的对映体和非对映体选择性环氧化。在肽序列中引入疏水和庞大的非天然氨基酸3-（1-吡啶基）丙氨酸可有效提高反应速度和对映选择性。
• A new and efficient catalytic isomerization of cis - and trans -epoxides
  作者：Ching-Yu Lo、Sitaram Pal、Arjan Odedra、Rai-Shung Liu

  DOI：10.1016/s0040-4039(03)00465-9

  日期：2003.4

  We report new ruthenium-catalyzed cis–trans isomerization of various functionalized epoxides. Enantiospecific isomerization of chiral epoxides is achieved without loss of enantiopurity, and epimerization occurs only at the epoxide carbon of the activating group.

  我们报告了新型钌催化的各种官能化环氧化物的顺式-反式异构化。实现手性环氧化物的对映体特异性异构化而不会损失对映体纯度，并且差向异构化仅在活化基团的环氧基碳上发生。
• New chiral amino alcohol ligands for catalytic enantioselective addition of diethylzincs to aldehydes
  作者：Carla Sappino、Alessandra Mari、Agnese Mantineo、Mauro Moliterno、Matteo Palagri、Chiara Tatangelo、Lorenza Suber、Paolo Bovicelli、Alessandra Ricelli、Giuliana Righi

  DOI：10.1039/c8ob00165k

  日期：——

  applicability as chiral catalysts was evaluated by carrying out the same reaction on a family of aldehydes, including variously substituted aromatic ones as well as an aliphatic analogue. The results have confirmed the validity of the fine-tuning process performed on ligands 13a and 13b. In fact, both exhibited excellent catalytic activity as demonstrated by the chemical yields and ee obtained from all the

  已经进行了旨在合成和优化具有适合于固定在磁铁矿纳米颗粒上的结构的新型，光学活性的β-氨基醇配体的结构的研究。优化的均相氨基醇催化剂13a和13b的手性来自合适的烯丙醇的Sharpless环氧化反应，通过使用公认的对映选择性氨基醇促进的二乙基锌与苯甲醛的加成反应进行测试，得到相应的苯甲醇，收率基本定量，ee = 95％。然后，通过对一系列醛，包括各种取代的芳族醛以及脂族类似物进行相同的反应，评估了它们作为手性催化剂的广泛适用性。结果证实了对配体13a和13b进行的微调过程的有效性。。实际上，如从化学产率和从所有测试的醛获得的ee所证实的，两者均显示出优异的催化活性，几乎与芳环中取代的位置和类型无关。
• Stereocontrolled synthesis of carbocyclic compounds with a quaternary carbon atom based on SN2′ alkylation of γ,δ-epoxy-α,β-unsaturated ketones
  作者：Fumihiko Yoshimura、Ayano Kowata、Keiji Tanino

  DOI：10.1039/c2ob25719j

  日期：——

  We developed a new method for stereoselective construction of an all-carbon quaternary stereogenic center on a carbocyclic ring based on regio- and stereoselective SN2′ alkylation reactions of γ,δ-epoxy-α,β-unsaturated cyclic ketones. Treatment of the ketones, which were readily prepared in enantiomerically pure form by means of aldol condensations between 3-ethoxy-2-cycloalkenones and α,β-epoxy aldehydes

  我们开发了一种新方法，用于基于γ，δ-环氧-α，β-不饱和环酮的区域和立体选择性S N 2'烷基化反应，在碳环上立体选择性构建全碳四元立体中心。用R 2 Zn-CuCN试剂处理酮，很容易以对映体纯的形式通过3-乙氧基-2-环烯酮和α，β-环氧醛之间的醛醇缩合制备酮，得到抗-S N 2'产物。立体选择性地。相反，相应的syn -S N通过对相同的γ，δ-环氧-α，β-不饱和环状酮进行两步转化来立体选择性地获得2'产物：（1）通过用MgCl 2处理将环氧部分转化为氯醇，以及（2）随后的S用R 2 Zn-CuCN试剂对氯醇进行N 2'取代。这些具有手性反式烯丙基醇部分的取代产物是复杂分子的有前途的前体。例如，一种取代产物的Eschenmoser-Claisen重排导致具有连续的四级和三级立体生成中心的酮酰胺的立体选择性形成。
• Stereoselective aldol condensation of boron enolates to trans α,β-epoxy aldehydes
  作者：Giuliana Righi、Francesca Spirito、Carlo Bonini

  DOI：10.1016/s0040-4039(02)00914-0

  日期：2002.7

  A study on the addition of boron enolates of methyl ketones to trans α,β-epoxy aldehydes is reported. The reaction proceeds with an excellent anti stereoselectivity, consistent with the Felkin–Ahn model, toward the synthesis of hydroxylated compounds with defined stereochemistry.

  报道了将甲基酮的烯醇硼酸酯加到反式α，β-环氧醛中的研究。该反应以符合Felkin-Ahn模型的出色的抗立体选择性进行，可合成具有确定立体化学的羟基化化合物。