(Z)-戊-2-烯-1-基苯甲酸酯 | 65466-10-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: (Z)-戊-2-烯-1-基苯甲酸酯
• 英文名称: (Z)-pent-2-en-1-yl benzoate
• 英文别名: (Z)-2-penten-1-yl benzoate；[(Z)-pent-2-enyl] benzoate
• CAS: 65466-10-6
• 化学式: C₁₂H₁₄O₂
• 分子量: 190.242
• InChiKey: CSDCIXOZTUVBQA-CLTKARDFSA-N

物化性质

• LogP：
  4.078 (est)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 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：

  (Z)-戊-2-烯-1-基苯甲酸酯 在 叔丁基过氧化氢 、 silver hexafluoroantimonate 、 二氯[2-(4,5-二氢-2-噁唑基)喹啉]钯(II) 作用下， 以 二氯甲烷 、 水 为溶剂， 以31%的产率得到3-oxopentyl benzoate
  参考文献：
  名称：

  Wacker-Type Oxidation of Internal Alkenes using Pd(Quinox) and TBHP

  摘要：

  The Pd-catalyzed TBHP-mediated Wacker-type oxidation of internal alkenes is reported. The reaction uses 2(4,5-dihydro-2-oxazolyl)quinoline (Quinox) as ligand and TBHP(aq) as oxidant to deliver single ketone constitutional isomer products in a predictable fashion from electronically biased olefins. This methodology is showcased through its application on an advanced intermediate in the total synthesis of the antimalarial drug artemisinin.

  DOI：

  10.1021/jo302638v
• 作为产物：
  描述：

  N-苯甲酰咪唑 、 顺-2-戊烯醇 在 吡啶盐酸盐 作用下， 以 乙腈 为溶剂， 反应 24.0h， 以82%的产率得到(Z)-戊-2-烯-1-基苯甲酸酯
  参考文献：
  名称：

  Dual Brønsted Acid/Nucleophilic Activation of Carbonylimidazole Derivatives

  摘要：

  Carbonylimidazole derivatives have been found to be highly active acylation reagents for esterification and amidation in the presence of pyridinium salts. These reactions are thought to involve both Bronsted acid and nucleophilic catalysis. This mode of activation has been applied to the synthesis of difficult to access oxazolidinones, as well as esters and amides. Finally, the use of pyridinium salts has been shown to accelerate the esterification of carboxylic acids with imidazole carbamates.

  DOI：

  10.1021/ol300339q

文献信息

• PROCESS FOR THE SYNTHESIS OF KETONES FROM INTERNAL ALKENES
  申请人：CALIFORNIA INSTITUTE OF TECHNOLOGY

  公开号：US20140194604A1

  公开（公告）日：2014-07-10

  The present invention is directed to methods for oxidizing internal olefins to ketones. In various embodiments, each method comprising contacting an organic substrate, having an initial internal olefin, with a mixture of (a) a biscationic palladium salt; and (b) an oxidizing agent; dissolved or dispersed in a solvent system to form a reaction mixture, said solvent system comprising at least one C 2-6 carbon nitrile and optionally at least one secondary alkyl amide, said method conducted under conditions sufficient to convert at least 50 mol % of the initial internal olefin to a ketone, said ketone positioned on a carbon of the initial internal olefin. The transformation occurs at room temperature and shows wide substrate scope. Applications to the oxidation of seed oil derivatives and a bioactive natural product are described.

  本发明涉及将内烯烃氧化为酮的方法。在各种实施方式中，每种方法包括将具有初始内烯烃的有机底物与（a）双阳离子钯盐的混合物；和（b）氧化剂接触，溶解或分散在溶剂体系中形成反应混合物，所述溶剂体系包括至少一种C2-6碳腈和可选地至少一种次烷基酰胺，所述方法在足以将初始内烯烃的至少50摩尔％转化为酮的条件下进行，所述酮位于初始内烯烃的碳上。该转化在室温下发生，并显示出广泛的底物范围。描述了将其应用于种子油衍生物和生物活性天然产物的氧化。
• [(<i>p</i>-Cymene)RuCl₂]₂: An Efficient Catalyst for Highly Regioselective Allylic Alkylations of Chelated Amino Acid Ester Enolates
  作者：Anton Bayer、Uli Kazmaier

  DOI：10.1002/chem.201402825

  日期：2014.8.11

  are excellent nucleophiles for ruthenium‐catalyzed allylic alkylations. Although [Cp*Ru(MeCN)3]PF6 was found to be the most reactive catalyst investigated, with the resulting allyl complexes reacting at temperatures as low as −78 °C, unfortunately the process took place with only moderate regio‐ and diastereoselectivity. In contrast, [(p‐cymene)RuCl2]2 allowed allylations to be performed with a high degree

  螯合的氨基酸酯烯醇盐是钌催化的烯丙基烷基化反应的优良亲核试剂。尽管发现[Cp * Ru（MeCN）3 ] PF 6是最活泼的催化剂，但生成的烯丙基络合物在低至-78°C的温度下反应，但不幸的是，该过程仅在区域和非对映选择性中等。相反，[（p- cymene）RuCl 2 ] 2允许烯丙基化具有高度的区域保留性。发现具有末端双键的仲烯丙基羧酸盐是反应性最强的底物，产生具有完美的区域保留和手性转移的支链氨基酸。在这种情况下，与类似物钯配合物相比，未观察到原位形成的Ru-烯丙基配合物的异构化。这个自由异构化协议也可以被用于（合成Ž）构型γ，δ不饱和氨基酸衍生物，从（起始ž）-烯丙基底物。在这里，发现活性更高的磷酸盐优于羧酸盐，以几乎定量的产量提供所需的氨基酸，并具有良好的区域和立体保留能力。因此，Ru催化的烯丙基化反应可以很好地克服Pd催化方法的缺点。
• Stereoselective preparation of (E)-allyl alcohols via radical elimination from anti-γ-phenylthio-β-nitro alcohols
  作者：Akio Kamimura、Noboru Ono

  DOI：10.1039/c39880001278

  日期：——

  Phenylthio and hydroxymethyl groups may be introduced into nitroalkenes stereoselectively by treatment with benzenethiol and aqueous formaldehyde to give anti-γ-phenylthio-β-nitro alcohols, which are converted into (E)-allyl alcohols via radical elimination induced by Bu3SnH.

  苯硫基和羟甲基可立体选择性地通过与苯硫酚和甲醛水溶液，得到处理而引入硝基烯烃抗-γ苯硫基β硝基醇，其被转换成（ë） -烯丙基醇通过由卜诱导自由基清除3 SNH。
• US9096519B2
  申请人：——

  公开号：US9096519B2

  公开（公告）日：2015-08-04
• Dual Brønsted Acid/Nucleophilic Activation of Carbonylimidazole Derivatives
  作者：Stephen T. Heller、Tingting Fu、Richmond Sarpong

  DOI：10.1021/ol300339q

  日期：2012.4.20

  Carbonylimidazole derivatives have been found to be highly active acylation reagents for esterification and amidation in the presence of pyridinium salts. These reactions are thought to involve both Bronsted acid and nucleophilic catalysis. This mode of activation has been applied to the synthesis of difficult to access oxazolidinones, as well as esters and amides. Finally, the use of pyridinium salts has been shown to accelerate the esterification of carboxylic acids with imidazole carbamates.