2E-5-hydroxy-5-phenyl-pent-2-enoic acid ethyl ester | 114996-07-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 2E-5-hydroxy-5-phenyl-pent-2-enoic acid ethyl ester
• 英文别名: ethyl (2E)-5-hydroxy-5-phenyl-2-pentenoate；Ethyl 5-hydroxy-5-phenylpent-2-enoate；ethyl 5-hydroxy-5-phenyl-2-pentenoate；(+/-)-1-hydroxy-1-phenyl-penten-(3t)-oic acid-(5)-ethyl ester；(+/-)-1-Hydroxy-1-phenyl-penten-(3t)-saeure-(5)-aethylester；ethyl (E)-5-hydroxy-5-phenylpent-2-enoate
• CAS: 114996-07-5
• 化学式: C₁₃H₁₆O₃
• 分子量: 220.268
• InChiKey: CIWMXKRPVADVDK-UXBLZVDNSA-N

物化性质

• 沸点：
  353.5±42.0 °C(Predicted)
• 密度：
  1.100±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 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：

  2E-5-hydroxy-5-phenyl-pent-2-enoic acid ethyl ester 在 二异丁基氢化铝 作用下， 以68%的产率得到(2E)-5-phenylpent-2-ene-1,5-diol
  参考文献：
  名称：

  以环状氨基甲酸酯保护的 1,3-氨基醇的立体选择性方法：动力学与热力学控制

  摘要：

  描述了对被保护为环状氨基甲酸酯的 1,3-氨基醇的直接对映控制访问。该方法基于在 10% 的 Carreira 催化剂存在下将二烯醇甲硅烷基酯添加到醛中（添加乙烯基向山醛醇）。获得的δ-羟基酯被还原为戊-2-烯-1,5-二醇，其与异氰酸甲苯基酯一起转化为相应的二氨基甲酸酯。这些二氨基甲酸酯的立体选择性环化在热力学或动力学控制下进行 1,3-不对称诱导，以提供对映选择性六元环环状氨基甲酸酯。计算使我们能够合理化观察到的立体选择性。((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)。

  DOI：

  10.1002/ejoc.200700503
• 作为产物：
  描述：

  ethyl 2-(α-hydroxybenzyl)-3-butenoate 在 In(OSO₂CF₃)3 作用下， 以 二氯甲烷 为溶剂， 以19%的产率得到2E-5-hydroxy-5-phenyl-pent-2-enoic acid ethyl ester
  参考文献：
  名称：

  The First In(OTf)3-Catalyzed Conversion of Kinetically Formed Homoallylic Alcohols into the Thermodynamically Preferred Regioisomers: Application to the Synthesis of 22α-Sterols

  摘要：

  A retro-ene reaction that generates the parent aldehyde and a sigmatropic rearrangement are involved in the In(OTf)3 -catalyzed conversion of homoallylic alcohols 1 into the thermodynamically favored regioisomers 2. This method can be used for the stereocontrolled synthesis of linear homoallylic 22α-sterols from their readily accessible branched 22β isomers.

  DOI：

  10.1002/1521-3773(20010803)40:15<2921::aid-anie2921>3.0.co;2-v

文献信息

• Catalytic Nucleophilic Allylation Driven by the Water–Gas Shift Reaction
  作者：Scott E. Denmark、Zachery D. Matesich、Son T. Nguyen、Selena Milicevic Sephton

  DOI：10.1021/acs.joc.7b02658

  日期：2018.1.5

  of this reaction from the initial serendipitous discovery to its general synthetic scope is detailed, highlighting the roles of water, CO, and amine in the generation of a more complete catalytic cycle. The use of unsymmetrical allylic pro-nucleophiles was shown to give preferential product formation through the modulation of reaction conditions. Both (E)-cinnamyl acetate and vinyl oxirane were efficiently

  钌与烯丙基亲核试剂的醛催化烯丙基化已被证明是在温和条件下形成碳-碳键的有效方法。此反应从最初的偶然发现到其一般合成范围的演变过程都进行了详细介绍，突出了水，一氧化碳和胺在更完整的催化循环生成中的作用。结果表明，使用不对称的烯丙基亲核亲核试剂可以通过调节反应条件来优先形成产物。（E）-肉桂酸乙酸酯和乙烯基环氧乙烷均有效地用于形成抗支链产物（抗/ syn最高> 20：1 ）和E-线性产物（最高> 20：1 E / s ）Z）分别与芳香族，α，β-不饱和和脂肪族醛形成高选择性。强调了使反应对映选择性的尝试，包括对苯甲醛高达75:25的对映富集。
• Allylation of Carbonyl Compounds Mediated by Aluminum/Fluoride Salts in Water
  作者：Shizhen Yuan、Jin Liu、Ling Xu、Shaofeng Zhu

  DOI：10.1002/cjoc.201090115

  日期：——

  A novel mediator (Al/KF) has been developed and employed in the Barbier‐type alkylations of various aldehydes and ketones with alkyl halide in water. The carbonyl compounds could be effectively converted into corresponding homoallylic alcohol in good yields only when allyl bromides or substituted allyl bromides were used as halides. Aromatic aldehydes could afford homoallylic alcohols in high yields

  已经开发了一种新型介体（Al / KF），并将其用于水中烷基卤与各种醛和酮的Barbier型烷基化。仅当使用烯丙基溴或取代的烯丙基溴作为卤化物时，羰基化合物才能有效地有效地转化为相应的均丙醇。芳香醛可以提供高收率的均丙醇，但不幸的是，在相同条件下，被硝基或氨基取代的芳香醛的烯丙基化不能顺利进行，酮和脂肪族羰基化合物的烯丙基化产率较低。还研究了反应的非对映选择性和区域选择性，主要产物优先选择赤型或反型异构体。通过使用Al / KF介导的苯甲醛与肉桂酸溴化物和4-溴-2-丁烯酸乙酯的水溶液进行γ加合物。
• High regio- and stereoselective Barbier reaction of carbonyl compounds mediated by NaBF4/Zn (Sn) in waterElectronic supplementary information (ESI) available: spectral data of Barbier-type reaction products and quantum calculation results. See http://www.rsc.org/suppdata/nj/b3/b303187j/
  作者：Zhenggen Zha、Zhen Xie、Cunliu Zhou、Mingxin Chang、Zhiyong Wang

  DOI：10.1039/b303187j

  日期：——

  (M=Zn or Sn) showed that this novel mediator facilitated allylation of a variety of carbonyl compounds in water and had a great influence on the diastereoselectivity of the addition. More importantly, α- and γ-addition products of crotylations can be alternatively obtained under the control of this novel mediator. A reaction mechanism is proposed based on our quantum calculation and experimental results

  用NaBF 4 / M（M = Zn或Sn）进行的研究表明，这种新型介体可促进多种金属的烯丙基化羰基化合物 在 水对加成的非对映选择性有很大影响。更重要的是，在这种新型介体的控制下，可以选择性地获得丙烯酰化的α-和γ-加成产物。根据我们的量子计算和实验结果，提出了一种反应机理。
• New and Stereoselective Synthesis of 1,4-Disubstituted Buten-4-ols (Homoallylic Alcohol α-Adducts) from the Corresponding γ-Isomers (3,4-Disubstituted Buten-4-ols) via an Acid-Catalyzed Allyl-Transfer Reaction with Aldehydes
  作者：Shin-ichi Sumida、Masanori Ohga、Junji Mitani、Junzo Nokami

  DOI：10.1021/ja990057p

  日期：2000.2.1

  from aldehydes via the usual reaction with common allylic metals 1, were converted to the corresponding α-adducts 6 by an acid-catalyzed allyl-transfer reaction. In the allyl-transfer reaction, anti- and syn-γ-adducts 3 gave E- and Z-α-adducts 6, respectively, and the optical purity of the γ-adducts 3 was transferred to the α-adducts 6 with >98%ee. This suggests that the allyl-transfer reaction proceeds

  高烯丙基醇 3 的 γ-加合物通过与常见烯丙基金属 1 的通常反应从醛衍生，通过酸催化的烯丙基转移反应转化为相应的 α-加合物 6。在烯丙基转移反应中，反-和顺-γ-加合物3分别得到E-和Z-α-加合物6，γ-加合物3的光学纯度转移到α-加合物6，>98 %ee。这表明烯丙基转移反应通过六元环状过渡态 [T] 立体选择性地进行。该反应由各种金属三氟甲磺酸盐以及路易斯酸和布朗斯台德酸催化。
• Synthetic applications of elementoorganic compounds of group 15 and 16. 85. Pentaalkyl stiboranes. 1. Synthesis of homobenzylic alcohols, homoallylic alcohols, homoallylic alcohols, ethyl 5-aryl-5-hydroxy-2-pentenoates, and .beta.-hydroxypropionic acid derivatives via pentaalkylstiboranes
  作者：Yaozeng Huang、Yi Liao

  DOI：10.1021/jo00004a010

  日期：1991.2

  Although pentaalkylstiboranes have long been known, their applications in organic synthesis have not been exploited. It has been found that quaternary stibonium salts (n-Bu3SbCH2E]+X- (E = Ph, CH = CH2, CH = CHCO2Et, CO2Et, CN; X = Br, I, BPh4) on treatment with RLi (R = n-Bu, t-Bu, Ph) afford pentaalkylstiboranes, n-Bu3Sb(R)CH2E, which react with aromatic aldehydes to give, after subsequent hydrolysis, homobenzylic alcohols, homoallylic alcohols, ethyl 5-aryl-5-hydroxypent-2-enoates, ethyl beta-aryl-beta-hydroxypropionates, and beta-aryl-beta-hydroxypropionitriles, respectively, in good to excellent yields. The reaction is chemoselective for aldehydes.