ethyl (2E,4E)-5-(2-thienyl)penta-2,4-dienoate | 113579-32-1

• 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: ethyl (2E,4E)-5-(2-thienyl)penta-2,4-dienoate
• 英文别名: ethyl (2E,4E)-5-(thiophen-2-yl)penta-2,4-dienoate；5t-[2]thienyl-penta-2t,4-dienoic acid ethyl ester；5t-[2]Thienyl-penta-2t,4-diensaeure-aethylester；ethyl (2E,4E)-5-thiophen-2-ylpenta-2,4-dienoate
• CAS: 113579-32-1
• 化学式: C₁₁H₁₂O₂S
• 分子量: 208.281
• InChiKey: SGWMGTOJXQRCGU-PHQNLGIASA-N

物化性质

• 沸点：
  334.1±25.0 °C(Predicted)
• 密度：
  1.138±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  54.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  ethyl (2E,4E)-5-(2-thienyl)penta-2,4-dienoate 在 lithium aluminium tetrahydride 、 三乙胺 作用下， 以 乙醚 为溶剂， 生成 (2E,4E)-5-(2-Thienyl)-2,4-pentadienyl acetate
  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
• 作为产物：
  描述：

  alkaline earth salt of/the/ methylsulfuric acid 在 草酸 作用下， 生成 ethyl (2E,4E)-5-(2-thienyl)penta-2,4-dienoate
  参考文献：
  名称：

  Carbonyl Derivatives of Thiophene. II. The Reformatsky Reaction with Bromine Compounds Other Than α-Bromoesters

  摘要：

  DOI：

  10.1021/ja01612a037

文献信息

• 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。
• Synthesis of .GAMMA.-Hydroxybutenolides Applying Crossed Aldol Condensation in the Presence of a Bulky Lewis Acid and Their Anti-tumor Activity
  作者：Yumiko Yamano、Yumi Fujita、Yukari Mizuguchi、Kimie Nakagawa、Toshio Okano、Masayoshi Ito、Akimori Wada

  DOI：10.1248/cpb.55.1365

  日期：——

  An improved synthesis of gamma-hydroxybutenolides 1a-d was achieved via crossed aldol condensation between aldehydes 2a-d and the protected gamma-hydroxy-beta-methylbutenolides 3 or 4 using the bulky Lewis acid, aluminum tris(2,6-diphenylphenoxide) (ATPH). Using this same methodology, the gamma-hydroxybutenolides 17a-d having various heteroaromatic rings were synthesized and their anti-tumor activities

  使用庞大的路易斯酸三（2,6-二苯酚铝）铝，通过醛2a-d与受保护的γ-羟基-β-甲基丁烯化物3或4之间的交叉羟醛缩合反应，可以提高γ-羟基丁烯化物1a-d的合成效率（ ATPH）。使用相同的方法，合成了具有各种杂芳族环的γ-羟基丁烯内酯17a-d，并评估了它们的抗肿瘤活性。
• Copper-catalyzed C–S direct cross-coupling of thiols with 5-arylpenta-2,4-dienoic acid ethyl ester
  作者：Rongrong Cai、Zhuoda Zhou、Qianqian Chai、Yueer Zhu、Runsheng Xu

  DOI：10.1039/c8ra05311a

  日期：——

  A selective copper (Cu)-catalyzed C–S bond direct cross-coupling of thiols with 5-arylpenta-2,4-dienoic acid ethyl ester was developed. Notably, various biologically active 5-phenyl-3-phenylsulfanylpenta-2,4-dienoic acid ethyl ester derivatives were efficiently synthesized under moderate conditions. Finally, a plausible Cu(I)/Cu(III) reaction mechanism was proposed.

  开发了选择性铜 (Cu) 催化的 C-S 键直接交叉偶联硫醇与 5-arylpenta-2,4-二烯酸乙酯。值得注意的是，各种具有生物活性的 5-苯基-3-苯基硫烷基五-2,4-二烯酸乙酯衍生物在温和条件下被高效合成。最后，提出了一种似是而非的Cu( I )/Cu( III )反应机理。
• Stereoselective synthesis of naturally occurring unsaturated amide alkaloids by a modified Ramberg–Bäcklund reaction
  作者：Yang Li、Yu Zhang、Zhi Huang、Xiaoping Cao、Kun Gao

  DOI：10.1139/v04-028

  日期：2004.5.1

  A convenient and rapid approach for the synthesis of naturally occurring unsaturated amide alkaloids 1a–1n by the recently developed one-flask Ramberg–Backlund reaction is described. The starting material was alcohol 3, which was transformed into thiolacetate 4 using the Mitsunobu reaction. In situ cleavage of acetyl moiety of 4, followed by alkylation of the resulting thiol with appropriate chloroacetamide

  描述了一种通过最近开发的单瓶 Ramberg??Backlund 反应合成天然存在的不饱和酰胺生物碱 1a??1n 的方便快捷的方法。起始原料是醇 3，使用 Mitsunobu 反应将其转化为硫代乙酸酯 4。4 的乙酰基部分的原位裂解，然后用合适的氯乙酰胺 5 将所得硫醇烷基化，提供硫化物 6。硫化物 6 氧化得到相应的砜 2。在氧化铝-存在下用二溴二氟甲烷处理砜 2二氯甲烷溶液中负载的氢氧化钾得到不饱和酰胺生物碱1a??1n。据我们所知，1e和1i的合成是首次报道。关键词：合成，不饱和酰胺生物碱，Ramberg??Backlund反应。
• 10.1002/chem.202401905
  作者：Manwar, Rina Raju、Balamurugan, Rengarajan

  DOI：10.1002/chem.202401905

  日期：——

  demonstrated as olefinating agents in the silver-catalyzed olefination of aryl and cinnamyl aldehydes to make α,β- and α,β,γ,δ-unsaturated esters with excellent E-selectivity. Trimethyl orthoformate plays a dual role by generating nucleophilic allenolate from propiolate and more electrophilic oxocarbenium ion from aldehyde to effect the reaction.

  丙炔酯已被证明可以作为银催化芳基醛和肉桂醛烯化反应中的烯化剂，以制备具有优异E选择性的 α,β- 和 α,β,γ,δ-不饱和酯。原甲酸三甲酯发挥双重作用，通过从丙炔酸生成亲核联烯酸和从醛生成更具亲电性的氧碳鎓离子来实现反应。