ethyl (E)-3-cyclopropyl-3-phenylacrylate | 64701-92-4

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: ethyl (E)-3-cyclopropyl-3-phenylacrylate
• 英文别名: ethyl (E)-3-cyclopropyl-3-phenylprop-2-enoate
• CAS: 64701-92-4
• 化学式: C₁₄H₁₆O₂
• 分子量: 216.28
• InChiKey: IMALOEKNEKPARA-RAXLEYEMSA-N

物化性质

• 沸点：
  318.0±12.0 °C(Predicted)
• 密度：
  1.103±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 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：

  ethyl (E)-3-cyclopropyl-3-phenylacrylate 在 维生素 B2 作用下， 以 乙腈 为溶剂， 反应 24.0h， 以94%的产率得到ethyl (Z)-3-phenylbut-2-enoate
  参考文献：
  名称：

  A Bio-Inspired, CatalyticE→ZIsomerization of Activated Olefins

  摘要：

  Herein, Nature's flavin-mediated activation of complex (poly)enes has been translated to a small molecule paradigm culminating in a highly (Z)-selective, catalytic isomerization of activated olefins using (-)-ribo-flavin (up to 99:1 Z/E). In contrast to the prominent Z -> E isomerization of the natural system, it was possible to invert the directionality of the isomerization (E -> Z) by simultaneously truncating the retinal scaffold, and introducing a third olefin substituent to augment A1,3-strain upon isomerization. Consequently, conjugation is reduced in the product chromophore leading to a substrate/product combination with discrete photophysical signatures. The operationally simple isomerization protocol has been applied to a variety of enone-derived substrates and showcased in the preparation of the medically relevant 4-substituted coumarin scaffold. A correlation of sensitizer triplet energy (ET) and reaction efficiency, together with the study of additive effects and mechanistic probes, is consistent with a triplet energy transfer mechanism.

  DOI：

  10.1021/jacs.5b07136
• 作为产物：
  描述：

  ethyl 2-cyclopropyl-6,7-dimethyl-4-oxido-2-phenyl-1,5,8-trioxa-4λ5-phosphaspiro[3.4]octane-3-carboxylate 生成 ethyl (E)-3-cyclopropyl-3-phenylacrylate
  参考文献：
  名称：

  BREUER E.; ZBAIDA S.; SEGALL E., TETRAHEDRON LETT., 1979, NO 24, 2203-2204

  摘要：

  DOI：

文献信息

• The Photochemistry of 2-Cyclopentenyl Methyl Ketones
  作者：Hans-Ulrich Gonzenbach、Inga-Mai Tegmo-Larsson、Jean-Pierre Grosclaude、Kurt Schaffner

  DOI：10.1002/hlca.19770600334

  日期：1977.4.20

  3-phenyl-2-cyclopentenyl methyl ketones (15–18, 30, 31) undergo a 1,3-acetyl shift on direct irradiation, and the oxa-di-π-methane rearrangement to photochemically non-interconverting endo and exo bicyclo-[2.1.0]pentyl methyl ketones on triplet sensitization. Exceptions include the 2-methyl-3-phenyl-2-cyclopentenyl methyl ketone 32 and the 1-phenyl-2-cyclo-pentenyl methyl ketone 44 which are unreactive

  2-环戊烯基和3-苯基-2-环戊烯基甲基酮（15-18、30、31）在直接辐照下发生1,3-乙酰基转移，并且氧-二-π-甲烷重排成光化学非互变内和外双环- [2.1.0]戊基甲基酮在三线态敏化。分别包括2-甲基-3-苯基-2-环戊烯基甲基酮32和1-苯基-2-环戊烯基甲基酮44，它们分别在直接照射和三重态敏化时不反应，而在2-苯基-在任何一种条件下都不反应的2-环戊烯基甲基酮42和43。3-苯基-2-环戊烯基甲基酮的反应性三重态通过比较刚性玻璃中其在77K处的磷光与1-苯基-环戊烯的磷光以及与量子点的独立性，可以确定30为E T = 59 kcal / mol的局域苯乙烯π，π* -态。敏化剂能量在61–74 kcal / mol的范围内。
• Catalytic hydrogenation of α,β-unsaturated carboxylic acid derivatives using copper(<scp>i</scp>)/N-heterocyclic carbene complexes
  作者：Birte M. Zimmermann、Sarah C. K. Kobosil、Johannes F. Teichert

  DOI：10.1039/c8cc09853k

  日期：——

  air-stable copper(I)/N-heterocyclic carbene complex enables the catalytic hydrogenation of enoates and enamides, hitherto unreactive substrates employing homogeneous copper catalysis and H2 as a terminal reducing agent. This atom economic transformation replaces commonly employed hydrosilanes and can also be carried out in an asymmetric fashion.

  简单且空气稳定的铜（I）/ N-杂环卡宾络合物能够实现烯酸酯和烯酰胺的催化氢化，这是迄今为止使用均相铜催化和H 2作为末端还原剂的非反应性底物。这种原子经济的转变代替了常用的氢硅烷，并且也可以以不对称的方式进行。
• Selective Synthesis of <i>Z</i> ‐Cinnamyl Ethers and Cinnamyl Alcohols through Visible Light‐Promoted Photocatalytic <i>E</i> to <i>Z</i> Isomerization
  作者：Hengchao Li、Hang Chen、Yang Zhou、Jin Huang、Jundan Yi、Hongcai Zhao、Wei Wang、Linhai Jing

  DOI：10.1002/asia.201901778

  日期：2020.3.2

  A photocatalytic E to Z isomerization of alkenes using an iridium photosensitizer under mild reaction conditions is disclosed. This method provides scalable and efficient access to Z-cinnamyl ether and allylic alcohol derivatives in high yields with excellent stereoselectivity. Importantly, this method also provides a powerful strategy for the selective synthesis of Z-magnolol and honokiol derivatives

  公开了在温和的反应条件下使用铱光敏剂的烯烃的光催化E至Z异构化。该方法提供了可扩展且有效的途径，以优异的立体选择性高产率地获得了Z-肉桂基醚和烯丙醇衍生物。重要的是，该方法还为选择性合成具有潜在生物活性的Z-厚朴酚和厚朴酚衍生物提供了强有力的策略。
• Copper(<scp>i</scp>)-catalysed asymmetric allylic reductions with hydrosilanes
  作者：T. N. Thanh Nguyen、Niklas O. Thiel、Johannes F. Teichert

  DOI：10.1039/c7cc07008j

  日期：——

  copper(I)-catalysed asymmetric allylic reduction enables a regio- and stereoselective transfer of a hydride nucleophile in an SN2′-fashion onto allylic bromides. This transformation represents a conceptually orthogonal approach to allylic substitution reactions with carbon nucleophiles. A copper(I) complex based upon a chiral N-heterocyclic carbene (NHC) ligand allows for stereoselectivity reaching 99% ee

  铜（I）催化的不对称烯丙基还原可实现S N 2'形式的氢化物亲核试剂的区域和立体选择性转移到烯丙基溴上。这种转变代表了与碳亲核试剂进行烯丙基取代反应的概念上正交的方法。基于手性N-杂环卡宾（NHC）配体的铜（I）配合物可使立体选择性达到99％ee。不管起始材料的双键构型如何，该催化剂都能进行立体收敛反应。
• Copper-Catalyzed Trifluoromethylation of Trisubstituted Allylic and Homoallylic Alcohols
  作者：Jian Lei、Xiaowu Liu、Shaolin Zhang、Shuang Jiang、Minhao Huang、Xiaoxing Wu、Qiang Zhu

  DOI：10.1002/chem.201406627

  日期：2015.4.27

  An efficient copper‐catalyzed trifluoromethylation of trisubstituted allylic and homoallylic alcohols with Togni’s reagent has been developed. This strategy, accompanied by a double‐bond migration, leads to various branched CF3‐substituted alcohols by using readily available trisubstituted cyclic/acyclic alcohols as substrates. Moreover, for alcohols in which β‐H elimination is prohibited, CF3‐containing

  已经开发了使用Togni试剂对三取代的烯丙基和均烯丙基醇进行有效的铜催化三氟甲基化反应。这种策略，伴随着双键迁移，通过使用现成的三取代的环状/无环醇作为底物，导致了各种支链CF 3-取代的醇。此外，对于禁止β-H消除的醇，含CF 3的氧杂环丁烷是唯一的产物。