(2E,4E)-ethyl 4-methyl-5-phenylpenta-2,4-dienoate | 58550-28-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (2E,4E)-ethyl 4-methyl-5-phenylpenta-2,4-dienoate
• 英文别名: ethyl (2E,4E)-4-methyl-5-phenylpenta-2,4-dienoate
• CAS: 58550-28-0
• 化学式: C₁₄H₁₆O₂
• 分子量: 216.28
• InChiKey: JEKMXSDPAAODCX-HULFFUFUSA-N

物化性质

• 沸点：
  106-110 °C(Press: 0.2 Torr)
• 密度：
  1.030±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.21
• 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：

  (2E,4E)-ethyl 4-methyl-5-phenylpenta-2,4-dienoate 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 甲基磺酰胺 、 potassium carbonate 吡啶 、 四氧化锇 、 甲酸 、 DHQ-2-Me-2-Quin 、 三乙胺 、 三苯基膦 、 potassium hexacyanoferrate(III) 作用下， 以 四氢呋喃 、 二氯甲烷 、 叔丁醇 为溶剂， 反应 10.25h， 生成 Ethyl (+/-)-(E)-(4R^*,5S^*)-5-hydroxy-4-methyl-5-phenyl-2-pentenoate
  参考文献：
  名称：

  De Novo Synthesis of 2-Substituted syn-1,3-Diols via an Iterative Asymmetric Hydration Strategy

  摘要：

  The enantioselective syntheses of several protected 4-substituted syn-3,5-dihydroxy carboxylic esters have been achieved from the corresponding achiral (E,E)- or (E,Z)-1,3-dienoates. The route relies upon an enantio- and regioselective Sharpless dihydroxylation and a palladium-catalyzed reduction to form gamma-substituted delta-hydroxy-1-enoates. The resulting delta-hydroxy-1-enoates are subsequently converted into benzylidene-protected 4-substituted syn-3,5-dihydroxy carboxylic esters in one step. The benzylidene-protected 3,5-dihydroxy carboxylic esters are produced in good overall yields (20-54%) and high enantiomeric excess (73- 97% ee).

  DOI：

  10.1021/jo061200h
• 作为产物：
  描述：

  乙酸乙酯 、 反式-alpha-甲基肉桂醛 生成 (2E,4E)-ethyl 4-methyl-5-phenylpenta-2,4-dienoate
  参考文献：
  名称：

  Novel synthesis of phenol derivatives by palladium-catalyzed cyclocarbonylation of 2,4-pentadienyl acetates

  摘要：

  Phenyl acetates were selectively obtained in good yields by cyclocarbonylation of 2,4-pentadienyl acetates in the presence of NEt3, Ac2O, and a catalytic amount of palladium complexes such as PdCl2(PPh3)2 at 120-140-degrees-C under 50 atm of CO. No five-membered ring products were observed. A platinum complex PtCl2(PPh3)2 was also effective as a catalyst. The reaction of 5-phenyl-2,4-pentadienyl bromide with M(CO)(PPh3)3 (M = Pd or Pt) under CO gave the corresponding 6-phenyl-3, 5-hexadienoyl complexes in a high yield, which in turn afforded 2-acetoxybiphenyl in 41-51% yield on heating to 160-degrees-C under 50 atm of CO in the presence of NEt3 and Ac2O. Similar 3,5-hexadienoyl complexes are proposed to be intermediates in the catalytic cyclocarbonylation of 2,4-pentadienyl acetates. On the other hand, PdCl2(PPh3)2-catalyzed carbonylation of o-(bromomethyl)(1-alkenyl)-benzenes in the presence of NEt3 and Ac2O gave 2-naphthyl acetates in moderate yields, while the reaction in the absence of Ac2O gave five-membered ring products such as 2-indanones or a tricyclic lactone by incorporation of one or two CO molecules, respectively.

  DOI：

  10.1021/jo00076a051

文献信息

• The stereochemistry of the intramolecular electrophilic attack of an aldehyde on a carbon-tin bond
  作者：Ian Fleming、Michael Rowley

  DOI：10.1016/s0040-4020(01)87383-x

  日期：1986.1

  The cyclopentane-forming reaction (20–43) of (4),5)-2, 2,4-trimethyl-5-trimethylstannylhexanal takes place with retention of configuration at the carbon atom undergoing electrophilic substitution, in contrast to similar cyclopropane-forming reactions (e.g. 47–48), which take place with inversion of configuration. The hydride transfer (24–45) of the 4,5 diastereoisomeric hexanal takes place from a conformation

  （4 ），5 ）-2，2,4-三甲基-5-三甲基锡烷基己醛的环戊烷形成反应（20–43）与亲电取代的碳原子形成相反，发生了亲电取代的碳原子上保留了构型反应（例如47–48），这是随着配置反转而发生的。4,5非对映异构己醛的氢化物转移（24-45）是从氢化物构象到苯乙烯基的。对于可能形成四元环的反应，会发生断裂（16–28和17–30）。带有苯乙烯基的碳上存在苯环会干扰旨在测试S E 2反应的立体化学的反应，从而使该反应转向形成四氢化萘（10-26和34-38）或苯环庚烯（34 –37）。
• Stereoselective synthesis of substituted all-trans 1,3,5,7-octatetraenes by a modified Ramberg–Bäcklund reaction
  作者：Xiao-Ping Cao

  DOI：10.1016/s0040-4020(01)01224-8

  日期：2002.2

  The reaction of allylic dienylic sulfone with dibromodifluoromethane in the presence of alumina-supported KOH in dichloromethane solution results in facile rearrangement affording the corresponding all-trans 1,3,5,7-octatetraenes in excellent yields. This result shows that the double bonds of stereochemically defined allylic dienylic sulfone retain their stereochemistry and the newly formed double

  烯丙基二烯基砜与二溴二氟甲烷在二氯甲烷溶液中的氧化铝负载KOH的反应导致容易的重排，从而以优异的收率提供了相应的全反式1,3,5,7-辛酸酯。该结果表明，在改良的Ramberg-Bäcklund方法中，立体化学定义的烯丙基二烯基砜的双键保留了其立体化学，新形成的双键具有（E）-构型。
• S_N2″-Selective and Enantioselective Substitution with Unsaturated Organoboron Compounds and Catalyzed by a Sulfonate-Containing NHC-Cu Complex
  作者：Yuebiao Zhou、Ying Shi、Sebastian Torker、Amir H. Hoveyda

  DOI：10.1021/jacs.8b10885

  日期：2018.12.5

  53-89% yield, 69-96% SN2″ selectivity, 98:2 to >98:2 E: Z ratio, and 94:6-98:2 er. Insight regarding several of the unique mechanistic attributes of the catalytic process was obtained on the basis of kinetic isotope effect measurements and DFT studies. These investigations indicate that cationic π-allyl-Cu complexes are likely intermediates, clarifying the role of the s-cis and s-trans conformers of

  公开了第一个广泛适用的 SN2" 选择性和对映选择性催化取代策略。转化由 5.0 mol% 的含磺酸盐的 NHC-Cu 复合物（NHC = N-杂环卡宾）促进，并在市售的烯基-B（pin）（pin = pinacolato）或易于获得的甲硅烷基保护的炔丙基-B(pin)。发现无环、或芳基-、杂芳基-和烷基取代的五-2,4-二烯基磷酸酯，以及仅带有1,2-二取代烯烃或1,2-二取代和三取代烯烃的那些是合适的起始材料。环状磷酸二烯酯也可用作底物。以 51-82% 的收率获得了除 1,3-二烯基外还含有易于官能化的炔丙基部分（来自与丙二烯基-B(pin) 的反应）的产物，84-97% SN2" 选择性，89:11-97:3 E: Z 比和 86:14-98:2 对映体比 (er)。与甲硅烷基保护的炔丙基-B(pin) 化合物反应导致形成相应的甲硅烷基-烯丙基产物，产率 53-89%，SN2" 选择性
• Cobalt-Catalyzed Diastereo- and Enantioselective Reductive Allyl Additions to Aldehydes with Allylic Alcohol Derivatives via Allyl Radical Intermediates
  作者：Lei Wang、Lifan Wang、Mingxia Li、Qinglei Chong、Fanke Meng

  DOI：10.1021/jacs.1c05690

  日期：2021.8.18

  enantioenriched homoallylic alcohols with a remarkably broad scope of allyl groups that can be introduced. Mechanistic studies indicated that allyl radical intermediates were involved in this process. These new discoveries establish a new strategy for development of enantioselective transformations through capture of radicals by chiral Co complexes, pushing forward the frontier of Co complexes for enantioselective

  催化生成两亲性 π-烯丙基-金属配合物及其在对映选择性转化中的应用构成了将烯丙基引入分子的有效方法。本文提出了一种前所未有的钴催化的高度位点、非对映和对映选择性方案，用于立体选择性形成亲核烯丙基-Co(II) 配合物，然后加入醛。该反应的特点是将容易获得的烯丙醇衍生物非对映和对映收敛转化为多样化的富含对映体的高烯丙醇，其中可以引入的烯丙基范围非常广泛。机理研究表明，烯丙基自由基中间体参与了这一过程。
• Expedient Synthesis of Fused Azepine Derivatives Using a Sequential Rhodium(II)-Catalyzed Cyclopropanation/1-Aza-Cope Rearrangement of Dienyltriazoles
  作者：Erica E. Schultz、Vincent N. G. Lindsay、Richmond Sarpong

  DOI：10.1002/anie.201405356

  日期：2014.9.8

  reported. The process involves an intramolecular cyclopropanation of an α‐imino rhodium(II) carbenoid, leading to a transient 1‐imino‐2‐vinylcyclopropane intermediate which rapidly undergoes a 1‐aza‐Cope rearrangement to generate fused dihydroazepine derivatives in moderate to excellent yields. The reaction proceeds with similar efficiency on gram scale. The use of catalyst‐free conditions leads to the formation

  报道了一种从带有系链二烯的 1-磺酰基-1,2,3-三唑形成稠合二氢氮杂卓衍生物的一般方法。该过程涉及 α-亚氨基铑 (II) 类卡宾的分子内环丙烷化，产生短暂的 1-亚氨基-2-乙烯基环丙烷中间体，该中间体迅速发生 1-氮杂-Cope 重排，以中等至优异的产率生成稠合二氢氮杂卓衍生物。该反应在克规模上以类似的效率进行。使用无催化剂条件导致形成新的 [4.4.0] 双环杂环。