(2RS,3RS)-4-(benzyloxy)-2,3-epoxybutan-1-al

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2RS,3RS)-4-(benzyloxy)-2,3-epoxybutan-1-al
• 英文别名: (2RS,3RS)-4-benzyloxy-2,3-epoxybutanal；cis-3-[(benzyloxy)methyl]-2-oxiranecarbaldehyde；4-benzyloxy-2,3-epoxybutanal；(±)-3-((benzyloxy)methyl)oxirane-2-carbaldehyde；(2SR,3SR)-4-(benzyloxy)-2,3-epoxybutanal；(2S,3S)-3-(phenylmethoxymethyl)oxirane-2-carbaldehyde
• 化学式: C₁₁H₁₂O₃
• 分子量: 192.214
• InChiKey: AOHLUAAULDSDPB-MNOVXSKESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  38.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2RS,3RS)-4-(benzyloxy)-2,3-epoxybutan-1-al 在 magnesium 作用下， 以 甲醇 为溶剂， 反应 2.5h， 生成 methyl (3E)-6-(benzyloxy)-5-hydroxy-3-hexenoate
  参考文献：
  名称：

  Reductive cleavage reaction of .gamma.-functionalized .alpha.,.beta.-unsaturated esters and halomethyls mediated with magnesium in methanol

  摘要：

  Reductive cleavage of various types of C-O and C-N bonds tethered to alpha,beta-unsaturated esters and halomethyls was mediated with magnesium in methanol, which provided a facile method for the synthesis of delta-hydroxy or delta-amino beta,gamma-unsaturated esters and allylic alcohols. Regardless of the geometry (E or Z) of the alpha,beta-unsaturated esters, 1a-b, 5a-c, 11, 13, and 23, the cleavage product obtained was exclusively the E isomer of the corresponding deconjugated hydroxy and amino esters. The steric bias and ring strain of 15, 17, and 21 gave rise to a product mixture of E and Z isomers.

  DOI：

  10.1021/jo00058a038
• 作为产物：
  描述：

  顺-4-苄氧基-2-丁烯-1-醇 在 间氯过氧苯甲酸 作用下， 生成 (2RS,3RS)-4-(benzyloxy)-2,3-epoxybutan-1-al
  参考文献：
  名称：

  γ-δ-环氧-α-β-不饱和酯与烷基硼酸的钯催化的立体有择环氧化物开环反应，导致γ-δ-邻位二醇的构型两次反转。

  摘要：

  描述了γ-δ-环氧-α-β-不饱和酯与烷基硼酸的钯催化的立体有择环氧化物开环反应，生成γ-δ-邻位二醇，该反应继续保持构型，即通过两个连续的S（N）2的过程，以高收率提供相应的γ，δ环硼酸盐。

  DOI：

  10.1039/b307390d

文献信息

• Asymmetric Formal <i>trans</i>-Dihydroxylation and <i>trans</i>-Aminohydroxylation of α,β-Unsaturated Aldehydes via an Organocatalytic Reaction Cascade
  作者：Łukasz Albrecht、Hao Jiang、Gustav Dickmeiss、Björn Gschwend、Signe Grann Hansen、Karl Anker Jørgensen

  DOI：10.1021/ja103538s

  日期：2010.7.7

  study demonstrates the first formal asymmetric trans-dihydroxylation and trans-aminohydroxylation of alpha,beta-unsaturated aldehydes in an organocatalytic multibond forming one-pot reaction cascade. This efficient process converts alpha,beta-unsaturated aldehydes into optically active trans-2,3-dihydroxyaldehydes and trans-3-amino-2-hydroxyaldehydes with the aldehyde moiety protected as an acetal. The

  这项研究证明了在有机催化多键形成一锅反应级联中，α、β-不饱和醛的第一次正式不对称反式二羟基化和反式氨基羟基化。这种有效的过程将 α,β-不饱和醛转化为光学活性的反式-2,3-二羟基醛和反式-3-氨基-2-羟基醛，醛部分被保护为缩醛。精心设计的一锅法通过形成 2,3-环氧和 2,3-氮丙啶醛中间体进行，随后参与新的 NaOMe 引发的重排反应，导致形成缩醛保护的反式-2,3-二羟基醛和反式-3-氨基-2-羟基醛以高度立体选择性的方式。有利地，该多键形成反应级联可以一锅法进行，从而最大限度地减少获得产品所需的手动操作和纯化程序的数量。此外，为了 α、β-不饱和醛的反式氨基羟基化，开发了一种使用 4-甲基-N-（甲苯磺酰氧基）苯磺酰胺作为氮源的新的对映选择性氮丙啶化方案。α，β-不饱和醛的正式反式二羟基化和反式氨基羟基化的机制通过各种调查（包括同位素标记研究）阐明。最后，获得的产品被用于合成许多重要的分子。开发了一种使用
• Organocatalytic asymmetric epoxidation and tandem epoxidation/Passerini reaction under eco-friendly reaction conditions
  作者：Anna Maria Deobald、Arlene G. Corrêa、Daniel G. Rivera、Márcio Weber Paixão

  DOI：10.1039/c2ob26247a

  日期：——

  An eco-friendly synthesis of highly functionalized epoxides and their incorporation into an organocatalytic multicomponent approach are reported. For this, a modified class of diarylprolinol silyl ethers was designed to enable high catalytic activity in an environmentally benign solvent system. The one-pot procedure showed great efficiency in promoting stereoselective multicomponent transformations in a tandem, ‘green’ fashion. Because of its non-residual, efficient and selective character, this synthetic design shows promise for large-scale applications in both diversity and target-oriented syntheses.

  报道了一种环保的高功能化环氧化物合成方法，并将其应用于有机催化多组分反应策略。为此，设计了一类改良的二芳基脯氨醇硅醚，以在环境友好的溶剂体系中实现高催化活性。该一步法程序非常有效，能够促进立体选择性多组分反应以连贯、环保的方式进行。由于其无残留、高效和选择性的特点，这种合成设计在多样的和目标导向的合成中具有大规模应用的潜力。
• Lithium hydroxide as base in the Wittig reaction. A simple method for olefin synthesis
  作者：R. Antonioletti、F. Bonadies、A. Ciammaichella、A. Viglianti

  DOI：10.1016/j.tet.2008.02.091

  日期：2008.5

  A mild and practical procedure for the Wittig olefination, promoted by lithium hydroxide and triphenylbenzyl phosphonium bromide, has been set up for the synthesis of stilbenes and styrenes. The experimental conditions allow aromatic, heteroaromatic, unsaturated and saturated aliphatic aldehydes to give final products in good yields.

  已经建立了由氢氧化锂和三苯基苄基溴化promote促进的Wittig烯烃化反应的温和且实用的方法，用于合成对苯二酚和苯乙烯。实验条件允许芳族，杂芳族，不饱和和饱和脂族醛以高收率得到最终产物。
• 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。
• Synthesis of Phostones via the Palladium-Catalyzed Ring Opening of Epoxy Vinyl Phosphonates
  作者：Giri Raj Gnawali、Nigam P. Rath、Christopher D. Spilling

  DOI：10.1021/acs.joc.9b00905

  日期：2019.7.5

  The reaction of epoxy aldehydes with tetraethyl methylenediphosphonate gave γ,δ-epoxy vinyl phosphonates. The palladium-catalyzed addition of primary alcohols gave the monoprotected diols as single diastereoisomers. The trans- and cis-epoxides lead to opposite (syn and anti) diastereoisomers of the addition products. The alkene of the vinyl phosphonates was subjected to hydrogenation, and the resulting

  环氧醛与亚甲基二膦酸四乙酯的反应生成γ，δ-环氧乙烯基膦酸酯。钯催化的伯醇的加成得到单保护的非对映异构体的单保护的二醇。该反式-与顺环氧化物导致相反（顺式和反）的加成产物的对映异构体。对乙烯基膦酸酯的烯烃进行氢化，然后将所得的饱和膦酸酯进行碱催化的环化反应，从而在磷原子上形成新的手性中心时，得到具有非常高非对映选择性的磷矿。