2-(3-acetoxy-1-propenyl)thiophene | 121724-94-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: 2-(3-acetoxy-1-propenyl)thiophene
• 英文别名: 3-(2-thienyl)allyl acetate；3-(thiophen-2-yl)allyl acetate；3-Thiophen-2-ylprop-2-enyl acetate；3-thiophen-2-ylprop-2-enyl acetate
• CAS: 121724-94-5
• 化学式: C₉H₁₀O₂S
• 分子量: 182.243
• InChiKey: ZRDSOYZBCTVJDG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  54.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2S)-2-氨基-3-苯基丙酸乙酯 、 2-(3-acetoxy-1-propenyl)thiophene 在 bis(η3-allyl-μ-chloropalladium(II)) 、 1,3-双(二苯基膦)丙烷 、 C₂₄H₂₂O₃Si 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 zinc(II) chloride 作用下， 以 甲苯 为溶剂， 反应 50.0h， 以50%的产率得到
  参考文献：
  名称：

  结合手性醛催化和过渡金属催化对氨基酸酯的对映选择性α-烯丙基烷基化

  摘要：

  手性醛首次与路易斯酸和过渡金属合理结合，形成三重催化体系。该助催化体系在 N-未保护氨基酸酯和乙酸烯丙酯的不对称 α-烯丙基化反应中表现出良好的催化活化和立体选择性控制能力。以良好的产率（高达 87%）和对映选择性（高达 96% ee）生成具有光学活性的 α,α-二取代 α-氨基酸 (α-AAs)。初步机制研究表明，手性醛 3f 既可作为有机催化剂通过形成席夫碱来激活氨基酸酯，也可作为配体通过与 π-烯丙基 Pd(II) 物种配位促进亲核攻击过程。

  DOI：

  10.1021/jacs.9b01910
• 作为产物：
  描述：

  3-(2-噻吩)丙烯酸 在 lithium aluminium tetrahydride 作用下， 生成 2-(3-acetoxy-1-propenyl)thiophene
  参考文献：
  名称：

  Photocoupling between Haloheterocyclic Derivatives and Arylalkenes and Arylalkynes: Instruments to Predict Reactivity

  摘要：

  Parameters useful to predict reactivity and regiochemical control of photocoupling reactions between haloheterocyclic derivatives and arylalkenes or arylalkynes have been studied. Electrochemical properties of arylalkenes and arylalkynes are shown to be useful to predict the reactivity of the substrates. However, oxidation potentials fail as reactivity indices if very fast photochemical processes are in competition with the observed complex formation between substrates and halogen atoms. The regiochemical behavior of the reaction can be estimated on the basis of dipoles of the reagents. In this case the assumptions that a reagent approaches the other on parallel planes and that the prevalent interaction is between the SOMO of the radical and the LUMO of the other reagent have been accepted.

  DOI：

  10.1021/jo00131a008

文献信息

• Hydroamination versus Allylic Amination in Iridium-Catalyzed Reactions of Allylic Acetates with Amines: 1,3-Aminoalcohols via Ester-Directed Regioselectivity
  作者：Seung Wook Kim、Thomas Wurm、Gilmar A. Brito、Woo-Ok Jung、Jason R. Zbieg、Craig E. Stivala、Michael J. Krische

  DOI：10.1021/jacs.8b05683

  日期：2018.7.25

  In the presence of a neutral dppf-modified iridium catalyst and Cs2CO3, linear allylic acetates react with primary amines to form products of hydroamination with complete 1,3-regioselectivity. The collective data, including deuterium labeling studies, corroborate a catalytic mechanism involving rapid, reversible acetate-directed aminoiridation with inner-sphere/outer-sphere crossover followed by turnover-limiting

  在中性 dppf 改性的铱催化剂和 Cs2CO3 存在下，线性烯丙基乙酸酯与伯胺反应形成具有完全 1,3-区域选择性的加氢胺化产物。包括氘标记研究在内的集体数据证实了一种催化机制，该机制涉及快速、可逆的醋酸盐导向氨基环化，内球/外球交叉，然后是由胺介导的限制营业额的原脱金属。
• Pd-Catalyzed Allylation of Imines to Access α-CF₃ -Substituted α-Amino Acid Derivatives
  作者：Michael Winter、Hyunwoo Kim、Mario Waser

  DOI：10.1002/ejoc.201901272

  日期：2019.11.14

  herein report a high yielding protocol for the direct α‐allylation of easily accessible trifluoropyruvate‐derived imines using Pd‐catalysis. The reaction gives access to a variety of different α‐allylated‐α‐CF3‐amino acids in a straightforward manner, starting from commercially available trifluoropyruvate. We also provide a proof‐of‐concept for an enantioselective protocol (up to er = 75:25) by using

  我们在此报告了一种使用 Pd 催化将易于获得的三氟丙酮酸衍生亚胺直接 α-烯丙基化的高产方案。该反应从市售的三氟丙酮酸开始，以直接的方式获得各种不同的 α-烯丙基化-α-CF3-氨基酸。我们还通过使用手性磷烷配体为对映选择性协议（高达 er = 75:25）提供了概念验证。
• Pd-Catalyzed Olefination of Furans and Thiophenes with Allyl Esters
  作者：Yuexia Zhang、Zejiang Li、Zhong-Quan Liu

  DOI：10.1021/ol203013p

  日期：2012.1.6

  A direct Pd(II)-catalyzed olefination of furans and thiophenes with allyl esters is demonstrated. Under the typical conditions, the dehydrogenative Heck coupling reactions of heteroarenes with allylic esters proceeded via a β-H elimination rather than a β-OAc elimination to give the corresponding γ-substituted allylic esters.

  证明了呋喃和噻吩与烯丙基酯的直接Pd（II）催化的烯化反应。在典型条件下，杂芳烃与烯丙基酯的脱氢Heck偶联反应通过β-H消除而不是β-OAc消除进行，得到相应的γ-取代的烯丙基酯。
• Dual Ni/Organophotoredox Catalyzed Allylative Ring Opening Reaction of Oxabenzonorbornadienes and Analogs
  作者：Abdoul G. Diallo、Déborah Paris、Djiby Faye、Sylvain Gaillard、Mark Lautens、Jean-Luc Renaud

  DOI：10.1021/acscatal.2c00512

  日期：2022.3.18

  A general approach for the allylation of oxa- and azabenzonorbornadienes is reported by merging organophotoredox and nickel catalysis. This methodology allowed the diastereoselective allylation of various heterocyclic alkene derivatives with a broader range of allylic acetate compounds compared to previously published procedures. Moreover, no air-sensitive organometallic species and no metal reductants

  通过合并有机光氧化还原和镍催化，报道了一种用于氧杂和氮杂苯并降冰片二烯烯丙基化的一般方法。与先前公布的程序相比，这种方法允许各种杂环烯烃衍生物与更广泛的烯丙基乙酸酯化合物进行非对映选择性烯丙基化。此外，开环不需要对空气敏感的有机金属物质和金属还原剂（例如锌或锰）。机理研究表明，开环是通过碳金属化过程进行的。
• Stereodivergent Construction of 1,3‐Chiral Centers via Tandem Asymmetric Conjugate Addition and Allylic Substitution Reaction
  作者：Jia‐Hao Xie、Yi‐Ming Hou、Zuolijun Feng、Shu‐Li You

  DOI：10.1002/anie.202216396

  日期：2023.3

  cyclohexanones bearing multi-continuous stereocenters by combining copper-catalyzed asymmetric conjugate addition of dialkylzinc reagents to cyclic enones with iridium-catalyzed asymmetric allylic substitution reaction. Good to excellent yields, diastereoselectivity and enantioselectivity can be obtained. The current reaction can achieve the stereodivergent construction of nonadjacent stereocenters.

  在此，我们报道了通过将铜催化的二烷基锌试剂不对称共轭加成环状烯酮与铱催化的不对称烯丙基取代反应相结合，合成具有多个连续立构中心的环己酮。可以获得良好到优异的产率、非对映选择性和对映选择性。目前的反应可以实现非相邻立体中心的立体发散构建。