1-penten-2-yl benzoate | 95865-57-9

• 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: 1-penten-2-yl benzoate
• 英文别名: pent-1-en-2-yl benzoate；Benzoesaeure-(pent-1-en-2-ylester)
• CAS: 95865-57-9
• 化学式: C₁₂H₁₄O₂
• 分子量: 190.242
• InChiKey: MTKYYYXYVSSCPZ-UHFFFAOYSA-N

物化性质

• 沸点：
  91 °C(Press: 4 Torr)
• 密度：
  1.010±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-penten-2-yl benzoate 在 bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate 、 C₄₆H₃₅NO₂P₂ 、 氢气 作用下， 以 四氢呋喃 为溶剂， 20.0 ℃ 、2.0 MPa 条件下， 反应 1.0h， 以84%的产率得到苯甲酸-1-甲基丁酯
  参考文献：
  名称：

  膦-亚磷酰胺配体对1-烷基乙烯基酯的高对映选择性Rh催化加氢

  摘要：

  MatPhos，是完成艰苦任务的理想伴侣：迄今为止，由于中等ee值和低活性，阻碍了1-烷基乙烯基酯的不对称氢化，现在可以使用ee值为96–99％的MatPhos / Rh催化剂来实现在低催化剂负载量（0.1-1 mol％）和温和条件（5-20​​ bar H 2，室温）下制备底物。水解后，可以高对映体纯度获得相应的手性仲烷基醇，为获得这一重要产品类别提供了一条通用而实用的途径。

  DOI：

  10.1002/chem.201303066
• 作为产物：
  描述：

  1-戊炔 、 苯甲酸 在 钌 作用下， 以 水 为溶剂， 反应 24.0h， 生成 1-penten-2-yl benzoate
  参考文献：
  名称：

  1-烷基乙烯基苯甲酸酯的高度对映选择性加氢：手性2-烷基醇的简单，非酶促途径

  摘要：

  走向手性！描述了通过使用带有P bearingOP配体的Rh催化剂对烯醇酯1的高度对映选择性催化氢化（参见方案； NBD ＝降冰片二烯）。该催化体系具有广泛的范围，并允许制备具有高对映选择性的各种带有各种烷基或苄基的手性酯2。这些酯可以很容易地转化为高度对映体富集的2-链烷醇。

  DOI：

  10.1002/chem.201303500

文献信息

• Regioselective Formation of Enol Esters from the Ruthenium-Catalyzed Markovnikov Addition of Carboxylic Acids to Alkynes
  作者：Janine Jeschke、Christian Gäbler、Heinrich Lang

  DOI：10.1021/acs.joc.5b02293

  日期：2016.1.15

  selectivities with up to 99% of the Markovnikov product were achieved. The electronic influence of the substrates on the reaction rate was quantified by Hammett plots. By the use of electron-rich alkynes or highly acidic carboxylic acids, the reaction rate could be increased. Hence, the addition of highly acidic pentafluorobenzoic acid to electron-rich 4-methoxyphenylacetylene can even be carried out

  钌络合物[Ru（CO）2（P（p -C 6 H 4 -X）3）2（O 2 CPh）2 ]（1a，X = CF 3 ; 1b，X = Cl; 1c，X = H ；1d，X = Me；1e，X = OMe）已成功应用于末端区域炔烃的区域选择性马尔可夫尼可夫加成反应，生成了有价值的烯醇酯。催化剂筛选显示出膦的电子性质对活性和选择性有重大影响。催化剂1a达到最高活性，具有最吸电子的膦配体。通过添加催化量的AgOTf，可以进一步提高选择性和活性。此外，Markovnikov产品的选择性高达99％。底物对反应速率的电子影响通过哈米特图定量。通过使用富电子炔烃或高酸性羧酸，可以提高反应速率。因此，甚至可以在25°C下在4小时内定量地向富含电子的4-甲氧基苯基乙炔中添加高酸性五氟苯甲酸。此外，在温和的反应条件下（25–70°C），可以分离出种类繁多的简单的，电子或空间上具有挑战性的底物，具有良好的产率，具有很高的区域选择性。
• Ruthenium(IV)-Catalyzed Markovnikov Addition of Carboxylic Acids to Terminal Alkynes in Aqueous Medium
  作者：Victorio Cadierno、Javier Francos、José Gimeno

  DOI：10.1021/om1010325

  日期：2011.2.28

  promote the selective Markovnikov addition of both aromatic and aliphatic carboxylic acids to a large variety of terminal alkynes, enynes, and diynes as well as propargylic alcohols. In this way, a wide number of enol esters and β-oxo esters could be synthesized in moderate to good yields under mild conditions (60 °C) in an aqueous medium.

  二聚的双（烯丙基）合钌（IV）配合物[的RuCl（μ-Cl）的（η 3：η 3 -C 10 ħ 16）} 2 ]（C 10 H ^ 16 = 2,7-二甲-2,6-二烯-1,8-二基）（5）和单核几个物种的反式-将[RuCl 2（η 3：η 3 -C 10 ħ 16）（L）]（L =二电子给体配体）（6）衍生的从5起已检查过使用水作为绿色反应介质将羧酸加成到末端炔烃上的催化剂。在活动和区域选择性方面的最佳结果与单核获得衍生物的反式-将[RuCl 2（η 3：η 3 -C 10 ħ 16）（PPH 3）]（6A），这是能够促进选择性Markovnikov加成芳族和脂族羧酸都可以用于各种末端炔烃，烯炔和二炔以及炔丙醇。以此方式，可以在温和条件下（60℃）在水性介质中以中等至良好的产率合成大量的烯醇酯和β-氧代酯。
• Rh(I)/DpenPhos catalyzed asymmetric hydrogenation of enol esters and potassium (E)-3-cyano-5-methylhex-3-enoate
  作者：Yan Liu、Zheng Wang、Kuiling Ding

  DOI：10.1016/j.tet.2012.05.096

  日期：2012.9

  class of modular chiral monodentate phosphoramidites were highly efficient for the asymmetric hydrogenation of enol esters bearing α-aryl or α-alkyl groups, to afford the corresponding hydrogenation products in high enantioselectivities (87–95% ee) and reactivities (turnover number up to 10,000). These ligands were also shown to be effective in Rh(I)-catalyzed asymmetric hydrogenation of the potassium

  一类模块化手性单齿亚磷酰胺的Rh（I）络合物对于带有α-芳基或α-烷基的烯醇酯的不对称氢化反应非常有效，从而可以提供高对映选择性（87-95％ee）的相应氢化产物。活动（周转数最多10,000）。这些配体还显示出在Rh（I）催化的（E）-3-氰基-5-甲基己基-3-烯酸酯的钾盐的Rh（I）催化的不对称氢化中有效，从而得到相应的产物（CI-1008的前体），并具有高达95％的ee，并且可以完成底物的完全转化。
• Ruthenium-catalyzed selective addition of carboxylic acids to alkynes. A novel synthesis of enol esters
  作者：Takeaki Mitsudo、Yoji Hori、Yasushi Yamakawa、Yoshihisa Watanabe

  DOI：10.1021/jo00387a024

  日期：1987.5
• Asymmetric Hydrogenation of 1-Alkyl and 1-Aryl Vinyl Benzoates: A Broad Scope Procedure for the Highly Enantioselective Synthesis of 1-Substituted Ethyl Benzoates
  作者：Patryk Kleman、Pedro J. González-Liste、Sergio E. García-Garrido、Victorio Cadierno、Antonio Pizzano

  DOI：10.1021/cs501402z

  日期：2014.12.5

  The enantioselective hydrogenation of enol esters of formula CH2=C(OBz)R with rhodium catalysts based on phosphine phosphite ligands (P-OP) has been studied. The reaction has a broad scope, and it is suitable for the preparation of products possessing a wide variety of R substituents. For the cases where R is a primary alkyl, high catalyst activity (S/C = 500) and enantioselectivities (95-99% ee) were obtained with a catalyst characterized by an ethane backbone and a PPh2 fragment. In contrast, for R = t-Bu, a catalyst possessing a benzene backbone provided the best results (97% ee). Derivatives with a cycloalkyl R substituent were particularly difficult substrates for this reaction. A broader catalyst screening was required for these substrates, which identified a catalyst possessing a P(m-xylyl)(2) fragment as the most appropriate one, affording enantioselectivities between 90 and 95% ee. Outstanding enantioselectivities (99% ee) and high catalyst activity (S/C = 500-1000) were also obtained in the case of substrates bearing a Ph or a fluoroaryl R substituent. In addition, the system is also appropriate for the preparation of other synthetically useful esters as those for R = benzyl, 2-phenylethyl or N-phthalimido alkyl chains. Likewise, the hydrogenation of divinyl dibenzoates proceeded with very high diastero- and enantioselectivity, generating rather low amounts of the meso isomer (3-6%). On the other hand, substrates with Br and MeO substituents at the phenyl benzoate ring, suitable for further functionalization, have also been examined. The results obtained indicate no detrimental effect of these substituents in the hydrogenation. Alternatively, the methodology has been applied to the highly enantioselective synthesis of deuterium isotopomers of 1-octyl benzoate bearing CDH2, CD2H, or CD3 fragments. Finally, as a practical advantage of the present system, it has been observed that the high performance of the catalysts is retained in highly concentrated solutions or even in the neat substrate, minimizing both the amount of solvent added and the volume of the reaction.