tert-butyl 2-phenylacrylate | 133025-60-2

• 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: tert-butyl 2-phenylacrylate
• 英文别名: Tert-butyl 2-phenylprop-2-enoate
• CAS: 133025-60-2
• 化学式: C₁₃H₁₆O₂
• 分子量: 204.269
• InChiKey: WYHRIFREAGFVMV-UHFFFAOYSA-N

物化性质

• 沸点：
  293.8±19.0 °C(Predicted)
• 密度：
  0.997±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 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：

  tert-butyl 2-phenylacrylate 在 potassium phosphate 、 potassium permanganate 、 1,4-bis((4S,5S)-1,3-bis(3,5-di-tert-butylbenzyl)-4,5-diphenylimidazolidin-2-ylidene)piperazine-1,4-diium dichloride 作用下， 以 甲基叔丁基醚 、 水 为溶剂， 生成 tert-butyl phenylglyoxylate
  参考文献：
  名称：

  Enantioselective Oxidation of Alkenes with Potassium Permanganate Catalyzed by Chiral Dicationic Bisguanidinium

  摘要：

  Chiral anion-controlled ion-pairing catalysis was demonstrated to be a wide-ranging strategy that can utilize a variety of cationic metal species. In a similar manner, we envision a complementary strategy using chiral cation in partnership with inorganic anionic metal salts. Herein, we report a chiral dicationic bisguanidinium-catalyzed asymmetric oxidation reaction of alkenes with potassium permanganate. Chiral induction is attributed to ion-pairing interaction between chiral cation and enolate anion. The success of the current permanganate oxidation reaction together with mechanistic insights should provide inspiration for expansion to other anionic metal salts and would open up new paradigms for asymmetric transition metal catalysis, phase-transfer catalysis, and ion-pairing catalysis.

  DOI：

  10.1021/jacs.5b05792
• 作为产物：
  描述：

  2-苯基丙烯酸 、 二碳酸二叔丁酯 在 4-二甲氨基吡啶 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 以95%的产率得到tert-butyl 2-phenylacrylate
  参考文献：
  名称：

  Enantioselective Oxidation of Alkenes with Potassium Permanganate Catalyzed by Chiral Dicationic Bisguanidinium

  摘要：

  Chiral anion-controlled ion-pairing catalysis was demonstrated to be a wide-ranging strategy that can utilize a variety of cationic metal species. In a similar manner, we envision a complementary strategy using chiral cation in partnership with inorganic anionic metal salts. Herein, we report a chiral dicationic bisguanidinium-catalyzed asymmetric oxidation reaction of alkenes with potassium permanganate. Chiral induction is attributed to ion-pairing interaction between chiral cation and enolate anion. The success of the current permanganate oxidation reaction together with mechanistic insights should provide inspiration for expansion to other anionic metal salts and would open up new paradigms for asymmetric transition metal catalysis, phase-transfer catalysis, and ion-pairing catalysis.

  DOI：

  10.1021/jacs.5b05792

文献信息

• Rhodium-Catalyzed Hydrocarboxylation of Olefins with Carbon Dioxide
  作者：Shingo Kawashima、Kohsuke Aikawa、Koichi Mikami

  DOI：10.1002/ejoc.201600338

  日期：2016.7

  excellent yields. In this catalytic process with carbon dioxide, intervention of the RhI–H species, which could be generated from the RhI catalyst and diethylzinc, was clarified. Significantly, the catalytic asymmetric hydrocarboxylation of α,β-unsaturated esters with carbon dioxide was also performed by employing a cationic rhodium complex possessing (S)-(–)-4,4′-bi-1,3-benzodioxole-5,5′-diylbis(diphenylphosphine)

  探索了在空气稳定的铑催化剂存在下，苯乙烯衍生物和 α,β-不饱和羰基化合物与 CO2 (101.3 kPa) 的催化加氢羧化反应。[RhCl(cod)]2 (cod = cyclooctadiene) 作为催化剂和二乙基锌作为氢化物源的组合允许有效的加氢羧化并以中等至极好的产率提供相应的α-芳基羧酸。在这个使用二氧化碳的催化过程中，可以从 RhI 催化剂和二乙基锌产生的 RhI-H 物种的干预得到澄清。值得注意的是，α,β-不饱和酯与二氧化碳的催化不对称加氢羧化反应也通过使用含有 (S)-(-)-4,4'-bi-1,3-benzodioxole-5 的阳离子铑络合物进行，5'-二基双（二苯基膦）[(S)-SEGPHOS] 作为手性二膦配体。通过确定产品的绝对构型，提出了一个合理的不对称归纳模型。
• Electrochemical reduction of fluoroalkyl sulfones for radical fluoroalkylation of alkenes
  作者：Xin Zhou、Chuanfa Ni、Ling Deng、Jinbo Hu

  DOI：10.1039/d1cc03258e

  日期：——

  Radical fluoroalkylation of alkenes has been developed by electrochemical reduction of fluoroalkyl sulfones. A series of electron-deficient alkenes readily undergo hydrofluoroalkylation in good to excellent yields. This chemistry represents the first example of electrochemical generation of fluoroalkyl radicals from sulfones, which are used for practical radical fluoroalkylation of organic compounds

  烯烃的自由基氟烷基化已经通过氟代烷基砜的电化学还原发展起来。一系列缺电子烯烃很容易进行氢氟烷基化，产率非常好。这种化学反应代表了从砜电化学产生氟烷基自由基的第一个例子，用于有机化合物的实际自由基氟烷基化。
• Quaternary Charge-Transfer Complex Enables Photoenzymatic Intermolecular Hydroalkylation of Olefins
  作者：Claire G. Page、Simon J. Cooper、Jacob S. DeHovitz、Daniel G. Oblinsky、Kyle F. Biegasiewicz、Alyssa H. Antropow、Kurt W. Armbrust、J. Michael Ellis、Lawrence G. Hamann、Evan J. Horn、Kevin M. Oberg、Gregory D. Scholes、Todd K. Hyster

  DOI：10.1021/jacs.0c11462

  日期：2021.1.13

  Intermolecular C-C bond-forming reactions are underdeveloped transformations in the field of biocatalysis. Here we report a photoenzymatic intermolecular hydroalkylation of olefins catalyzed by flavin-dependent 'ene'-reductases. Radical initiation occurs via photoexcitation of a rare high-order enzyme-templated charge-transfer complex that forms between an alkene, α-chloroamide, and flavin hydroquinone

  分子间CC键形成反应是生物催化领域尚未发展的转化。在这里，我们报道了由黄素依赖性“烯”还原酶催化的烯烃光酶分子间加氢烷基化。自由基引发是通过一种罕见的高阶酶模板电荷转移复合物的光激发而发生的，该复合物在烯烃、α-氯酰胺和黄素氢醌之间形成。这种独特的机制确保只有当两种底物都存在于蛋白质活性位点内时才会发生自由基形成。该活性位点可以控制自由基终止氢原子转移，从而能够合成对映体丰富的γ-立体酰胺。这项工作凸显了光酶催化通过以前未知的电子转移机制实现新的生物催化转化的潜力。
• Stabilization of Organic Materials
  申请人：Gerster Michele

  公开号：US20080269382A1

  公开（公告）日：2008-10-30

  The invention describes a process for stabilizing an organic material against oxidative, thermal or light-induced degradation, which comprises incorporating therein or applying thereto at least a compound of the formula (I) wherein the general symbols are as defined in claim 1 . The compounds of the formula I are especially useful as processing stabilizers for synthetic polymers.

  该发明描述了一种用于稳定有机材料抵抗氧化、热降解或光诱导降解的过程，其中包括将化合物（I）至少混入其中或应用于其中，其中通式中的一般符号如权利要求1所定义。通式I的化合物特别适用作合成聚合物的加工稳定剂。
• Enantio- and Diastereoselective 1,2-Additions to α-Ketoesters with Diborylmethane and Substituted 1,1-Diborylalkanes
  作者：Stephanie A. Murray、Jacob C. Green、Sanita B. Tailor、Simon J. Meek

  DOI：10.1002/anie.201603465

  日期：2016.7.25

  The catalytic enantioselective synthesis of boronate‐substituted tertiary alcohols through additions of diborylmethane and substituted 1,1‐diborylalkanes to α‐ketoesters is reported. The reactions are catalyzed by readily available chiral phosphine/copper(I) complexes and produce β‐hydroxyboronates containing up to two contiguous stereogenic centers in up to 99:1 e.r. and greater than 20:1 d.r. The utility

  据报道，通过在α-酮酸酯中添加二硼烷基甲烷和取代的1,1-二硼烷基烷烃，可以催化合成硼酸酯取代的叔醇。反应由容易获得的手性膦/铜（I）配合物催化，并产生β-羟基硼酸酯，其含高达99：1 er和大于20：1 dr的多达两个连续的立体异构中心。有机硼产品的实用性通过几种化学选择性功能化。有证据表明反应是通过对映体富集的α-硼烷基-铜烷基中间体发生的。