4-苯基-丁2-烯酸乙酯 | 559062-83-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 中文名称: 4-苯基-丁2-烯酸乙酯
• 中文别名: 4-苯基丁-2-烯酸乙酯
• 英文名称: ethyl (2Z)-4-phenyl-2-butenoate
• 英文别名: ethyl (2Z)-4-phenylbut-2-enoate；(Z)-ethyl 4-phenylbut-2-enoate；ethyl (Z)-4-phenyl-2-butenoate；ethyl (Z)-4-phenylbut-2-enoate；ethyl cis-4-phenyl-2-butenoate
• CAS: 559062-83-8
• 化学式: C₁₂H₁₄O₂
• 分子量: 190.242
• InChiKey: LYZBCBTUPJJIKA-POHAHGRESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 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：

  4-苯基-丁2-烯酸乙酯 在 Chiral ketone Oxone 、 四丁基硫酸氢铵 、 二异丁基氢化铝 、 potassium carbonate 作用下， 以 乙醚 、 acetate buffer 、 乙腈 为溶剂， 反应 2.0h， 生成 [(2R,3R)-3-(苯基甲基)环氧乙烷-2-基]甲醇
  参考文献：
  名称：

  A pH Study on the Chiral Ketone Catalyzed Asymmetric Epoxidation of Hydroxyalkenes

  摘要：

  A detailed study shows that the chiral ketone catalyzed asymmetric epoxidations of hydroxyalkenes are highly pH dependent. The lower enantioselectivity obtained at low pH is attributed to the substantial contribution of the direct epoxidation by Oxone. At high pH the epoxidation mediated by chiral ketone out-competes the racemic epoxidation, leading to higher enantioselectivity. The effective substrates include allylic alcohol, homoallylic alcohol, and bishomoallylic alcohol. In most cases, over 90% ee was obtained.

  DOI：

  10.1021/jo972106r
• 作为产物：
  描述：

  ethyl 2-diazo-4-phenylbutanoate 在 三(五氟苯基)硼烷 、 二甲基亚砜 作用下， 反应 4.0h， 以62%的产率得到4-苯基-丁2-烯酸乙酯
  参考文献：
  名称：

  三（五氟苯基）硼烷催化 α-重氮酯（α-重氮酰胺）与二甲基亚砜的氧插入反应

  摘要：

  已经开发了三（五氟苯基）硼烷催化的 α-重氮酯（α-重氮酰胺）与二甲亚砜的氧化反应。该反应在无金属条件下进行，得到一系列 α-酮酯和 α-酮酰胺。该协议的合成效用通过合成转换和放大合成来证明。

  DOI：

  10.1002/adsc.202101336

文献信息

• Oxidative addition of N-halosuccinimides to palladium(0): the discovery of neutral palladium(II) imidate complexes, which enhance Stille coupling of allylic and benzylic halides
  作者：Catherine M. Crawforth、Suzanne Burling、Ian J.S. Fairlamb、Anant R. Kapdi、Richard J.K. Taylor、Adrian C. Whitwood

  DOI：10.1016/j.tet.2005.06.080

  日期：2005.10

  mediate the Stille coupling of allylic and benzylic halides with alkenyl, aryl and allyl stannanes. In competition experiments between 4-nitrobromobenzene and benzyl bromide with a cis-stannylvinyl ester, (Ph3P)2Pd(N-Succ)Br preferentially cross-couples benzyl bromide, whereas with other commonly employed precatalysts 4-nitrobromobenzene undergoes preferential cross-coupling. Furthermore, preferential

  已经研究了由空气和湿气稳定的含有琥珀酰亚胺或邻苯二甲酰亚胺（亚氨酸酯）配体的钯（II）膦配合物介导的有机锡烷和有机卤化物的斯蒂勒偶联。已经开发出一种有效的合成路线，以合成几种含有琥珀酰亚胺和邻苯二甲酰亚胺配体的钯（II）配合物。顺式-溴代双（三苯基膦）（N-琥珀酰亚胺）钯（II）[（Ph 3 P）2 Pd（N -Succ）Br]被证明可介导烯丙基和苄基卤化物的Stille偶联与烯基，芳基和烯丙基锡烷。在4-硝基溴苯和苄基溴与顺式-锡烷基乙烯基酯（Ph 3 P）2的竞争实验中Pd（N -Succ）Br优先使苄基溴交联，而与其他常用的预催化剂4-硝基溴苯进行优先交叉偶联。此外，首次观察到失活的苄基溴优先于活化的苄基溴的反应。卤化物的类型和琥珀酰亚胺配体的存在对于有效的Stille偶联至关重要。还显示出膦配体的类型改变了钯（II）琥珀酰亚胺配合物的催化活性。
• Generation of Phosphoranes Derived from Phosphites. A New Class of Phosphorus Ylides Leading to High <i>E</i> Selectivity with Semi-stabilizing Groups in Wittig Olefinations
  作者：Varinder K. Aggarwal、J. Robin Fulton、Chris G. Sheldon、Javier de Vicente

  DOI：10.1021/ja029573x

  日期：2003.5.1

  Tosylhydrazones derived from aryl aldehydes react with t-BuOK, ClFeTPP, (MeO)3P, and aldehydes to furnish olefins with high E selectivity. These reactions occur through a Wittig-type pathway via the corresponding diazo compounds, metal carbenes and phosphorous ylides, with the water-soluble trimethyl phosphate as the byproduct. Similar reactions can also be performed using ethyl diazoacetate; however

  源自芳基醛的甲苯磺酰腙与 t-BuOK、ClFeTPP、(MeO)3P 和醛反应以提供具有高 E 选择性的烯烃。这些反应通过相应的重氮化合物、金属卡宾和磷叶立德通过 Wittig 型途径发生，副产物为水溶性磷酸三甲酯。使用重氮乙酸乙酯也可以进行类似的反应；然而，仅在 LiBr 存在下才观察到高 E 选择性。在这种情况下，该反应被认为是通过通过 Arbuzov 反应形成的膦酸阴离子发生的。因此，该烯化反应通过 Horner-Wadsworth-Emmons (HWE) 反应发生，但膦酸阴离子是在完全无碱的条件下生成的。
• Efficient and selective Stille cross-coupling of benzylic and allylic bromides using bromobis(triphenylphosphine)(N-succinimide)palladium(II)
  作者：Catherine M. Crawforth、Ian J.S. Fairlamb、Richard J.K. Taylor

  DOI：10.1016/j.tetlet.2003.11.014

  日期：2004.1

  [Pd(NCOC2H4CO)(PPh3)2Br] 1. Significantly, these reactions do not require the use of hexamethylphosphoramide (HMPA) as the solvent, or additional ligands, such as trifurylphosphine or triphenylarsine. Selectivity for benzyl bromide over bromobenzene is observed for precatalyst 1, against the precatalysts, bromobis(triphenylphosphine)(benzyl)palladium(II) and bis(triphenylphosphine)palladium(II) bromide.

  使用预催化剂[Pd（NCOC 2 H 4 CO）（PPh 3）2 Br] 1可以使烯丙基和苄基溴与有机锡烷交联。重要的是，这些反应不需要使用六甲基磷酰胺（HMPA）作为溶剂，也不需要使用其他配体，例如三糠基膦或三苯基ar。对于预催化剂1，观察到苄基溴对溴苯的选择性相对于预催化剂溴双（三苯基膦）（苄基）钯（II）和双（三苯基膦）钯（II）。
• Engaging Alkenyl Halides with Alkylsilicates via Photoredox Dual Catalysis
  作者：Niki R. Patel、Christopher B. Kelly、Matthieu Jouffroy、Gary A. Molander

  DOI：10.1021/acs.orglett.6b00024

  日期：2016.2.19

  Single-electron transmetalation via photoredox/nickel dual catalysis provides the opportunity for the construction of Csp3–Csp2 bonds through the transfer of alkyl radicals under very mild reaction conditions. A general procedure for the cross-coupling of primary and secondary (bis-catecholato)alkylsilicates with alkenyl halides is presented. The developed method allows not only alkenyl bromides and

  通过光氧化还原/镍双重催化进行单电子重金属化，可在非常温和的反应条件下通过烷基自由基的转移来构建C sp 3 –C sp 2键。提出了伯和仲（双-邻苯二酚）烷基硅酸盐与烯基卤化物交叉偶联的一般方法。所开发的方法不仅允许使用烯基溴化物和碘化物，而且还可以使用先前未充分开发的烯基氯。
• A multicomponent coupling strategy suitable for the synthesis of the triene component of the oxazolomycin antibioticsThis is one of a number of contributions from the current members of the Dyson Perrins Laboratory to mark the end of almost 90 years of organic chemistry research in that building, as all its current academic staff move across South Parks Road to a new purpose-built laboratory.
  作者：Paul G. Bulger、Mark G. Moloney、Paul C. Trippier

  DOI：10.1039/b306925g

  日期：——

  Concise and versatile routes suitable for the synthesis of three geometric isomers of an analogue of the left hand triene sub-unit of oxazolomycin are reported. A strategy based upon a key Heck reaction was unsuccessful, and this was traced to a combination of steric encumbrance and electronic deactivation of the alkene substrate. An alternative Stille coupling strategy, however, proved to be both versatile and high yielding, and is potentially applicable to the synthesis of analogues with variation both in the side-chain geometry and in the identity of the terminal aromatic or heteroaromatic residue.

  报道了适用于合成oxazolomycin左旋三烯子单元类似物的三种几何异构体的简明且多功能的路线。基于关键Heck反应的策略未能成功，这归因于烯烃底物的空间阻碍和电子失活。然而，另一种Stille偶联策略既多功能又高产，且有可能适用于合成侧链几何结构和末端芳香或杂芳香残基不同的类似物。