rac-(E)-ethyl 2-hydroxy-4-phenylbut-3-enoate | 91129-16-7

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂醇
• 英文名称: rac-(E)-ethyl 2-hydroxy-4-phenylbut-3-enoate
• 英文别名: ethyl (E)-2-hydroxy-4-phenylbut-3-enoate；ethyl 2-hydroxy-4-phenylbut-3-enoate
• CAS: 91129-16-7
• 化学式: C₁₂H₁₄O₃
• 分子量: 206.241
• InChiKey: VKJBHXYAEPBVRG-CMDGGOBGSA-N

物化性质

• 沸点：
  347.0±30.0 °C(Predicted)
• 密度：
  1.137±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  15
• 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：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  rac-(E)-ethyl 2-hydroxy-4-phenylbut-3-enoate 在 ruthenium trichloride 叔丁基过氧化氢 作用下， 以 水 、 丙酮 为溶剂， 反应 1.0h， 以64.9%的产率得到(E)-ethyl-2-oxo-4-phenylbut-3-enoate
  参考文献：
  名称：

  Tanaka, Masato; Kobayashi, Toshi-aki; Sakakura, Toshiyasu, Angewandte Chemie, 1984, vol. 96, # 7, p. 519 - 520

  摘要：

  DOI：
• 作为产物：
  描述：

  反-苯乙烯乙酸 在 dirhodium tetraacetate 、 ABSA 、 硫酸 、 水 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 乙醚 、 乙腈 为溶剂， 反应 4.5h， 生成 rac-(E)-ethyl 2-hydroxy-4-phenylbut-3-enoate
  参考文献：
  名称：

  A Stereospecific Access to Allylic Systems Using Rhodium(II)−Vinyl Carbenoid Insertion into Si−H, O−H, and N−H Bonds

  摘要：

  Rhodium-catalyzed decomposition of alpha-vinyldiazoesters in the presence of silanes, alcohols, ethers, amines, and thiols have been shown to produce the corresponding alpha-silyl, alpha-hydroxy, alpha-alkoxy, alpha-amino, and alpha-thioalkoxy esters in generally good yield with a complete retention of the stereochemistry of the double bond of the diazo precursor. An extension of the process in homochiral series has also been devised using either a chiral auxiliary attached to the ester function or achiral alpha-vinyldiazoesters and Doyle's chiral catalyst Rh-2(MEPY)(4). In the former approach, pantolactone as chiral auxiliary gave diastereoselectivities of up to 70%, while the second approach produced the desired allylsilane with ee as high as 72%. On the other hand, Rh-2(MEPY)(4)-catalyzed insertion into the O-H bond of water led to poor or no enantioselectivity in good agreement with recent literature reports.

  DOI：

  10.1021/jo961952j

文献信息

• Regio- and Stereospecific <i>C</i>- and <i>O</i>-Allylation of Phenols via π-Allyl Pd Complexes Derived from Allylic Ester Carbonates
  作者：Christopher A. Discolo、Alexander G. Graves、Donald R. Deardorff

  DOI：10.1021/acs.joc.6b02608

  日期：2017.1.20

  for the C- and O-allylation of phenols via a common π-allyl Pd complex. While O-allylation of phenols by this method is a well-recognized reaction of general utility, the associated para-selective C-allylation reaction is still in its infancy. Cationic π-allyl Pd intermediates, derived from allylic ester carbonates and palladium(0) catalyst, were found to undergo the Friedel–Crafts-type para-selective

  通过共同的π-烯丙基Pd络合物，已开发出两种互补的策略用于苯酚的C-和O-烯丙基化。尽管通过这种方法进行的酚的O-烯丙基化是公认的通用反应，但是相关的对位选择性C-烯丙基化反应仍处于起步阶段。发现衍生自烯丙基碳酸酯和钯（0）催化剂的阳离子π-烯丙基Pd中间体经历了9种不同酚的Friedel-Crafts型对选择性C-烯丙基化反应。这两个C-和O-在金属催化的区域和立体有向取代性1,3-移位后，可以得到高至极好收率的烯丙基化产物。还确定了控制进入任一烯丙基化产品的条件。最后，对两种烯丙基化产物之间建立的平衡的研究表明，O-烯丙基化的化合物是动力学产物，而C-烯丙基化的化合物是热力学产物。
• Studies on the stereoselective selenolactonization, hydroxy and methoxy selenenylation of α- and β-hydroxy acids and esters. Synthesis of δ- and γ-lactones
  作者：Carmela Aprile、Michelangelo Gruttadauria、Maria E Amato、Francesca D'Anna、Paolo Lo Meo、Serena Riela、Renato Noto

  DOI：10.1016/s0040-4020(03)00206-0

  日期：2003.3

  The diastereoselective synthesis of hydroxy substituted γ- and δ-lactones was accomplished following two approaches. A 5- or 6-endo cyclization promoted by electrophilic selenium reagents of α- or β-hydroxy acids and a 5- or 6-exo cyclization of hydroxy esters obtained through a diastereoselective hydroxy selenenylation reaction of α- or β-hydroxy esters. Moreover, the diastereoselective methoxy selenenylation

  羟基取代的γ-和δ-内酯的非对映选择性合成是通过两种方法完成的。的5-或6-内环化促进由α-或β羟基酸电硒试剂和一个5-或6-外通过α-或β-羟基酯的非对映选择性羟基硒烯化反应获得的羟基酯的环化。另外，对上述化合物的非对映选择性的甲氧基亚硒基化进行了研究，结果表明在羟基亚硒基化条件下不反应的化合物在甲氧基亚硒基化条件下产生了脱保护的二醇。通过制备不对称官能化的对称化合物证明了甲氧基亚硒基化方法的有用性。发现产率和选择性取决于取代基（经历亲核攻击的碳原子上的Ph或烷基），环化方式，动力学或热力学控制条件。在后一种情况下，硅胶起着重要作用。
• Mercuri-desilylation of chiral cyclopropylmethylsilanes
  作者：Yannick Landais、Liliana Parra-Rapado

  DOI：10.1016/0040-4039(95)02387-9

  日期：1996.2

  Mercuri-desilylation of cyclopropylmethylsilanes such as 1 has been shown to occur with high regioselectivity. The cyclopropane ring-opening followed by desilylation proceeds stereospecifically to afford the corresponding olefins in good yields. The mercuri-mediated opening of cyclopropylmethyl alcohol analogues gives the opposite regioselectivity and affords only the tetrahydrofuran through a 5-endo-trig

  环丙基甲基硅烷（如1）的巯基去甲硅烷基化反应具有很高的区域选择性。环丙烷开环然后进行甲硅烷基化以立体定向进行，从而以良好的收率得到相应的烯烃。巯基介导的环丙基甲醇类似物的打开提供了相反的区域选择性，并通过5-内-trig环化仅提供了四氢呋喃。
• NAD(P)H Models 20
  作者：Louis H.P. Meijer、Upendra K. Pandit

  DOI：10.1016/s0040-4020(01)96440-3

  日期：1985.1

  reduced by NAD(P)H models (1-n-propyl-1,4-dihydronicotinamide (4) and Hantzsch ester(5)), in presence of magnesium perchlorate. One equivalent of the reductant reduces the substrates selectively to the corresponding 2-oxo-4-arylbutanoates (6,10a,b). An additional equivalent and higher temperature, converts ethyl 2-oxo-4-phenylbutanoate (6) to ethyl 2-hydroxy-4-phenylbutanoate (7). Reduction of ethyl

  NAD（P）H模型（1-正丙基-1,4-二氢烟碱酰胺（4）和Hantzsch酯（5））还原了2-氧代-4-芳基-3-丁烯-1-酸乙酯1a – 1c，在高氯酸镁存在下。还原剂的一个当量选择性降低了底物相应的2-氧代-4- arylbutanoates（6，图10A，b）。额外的当量和更高的温度将2-氧代-4-苯基丁酸乙酯（6）转化为2-羟基-4-苯基丁酸乙酯（7）。Hantzsch酯在C 2 H 5中还原2-氧代-4-苯基-3-苯基-3-丁烯-1-油酸乙酯（1a）OD或通过汉奇酯-4,4- d 2用C 2 ħ 5 OH，导致直接转移的氢或氘，分别的，而不加扰同位素。这些结果已被解释为支持氢化物转移机理。
• Synthesis of Chiral α,β-Unsaturated γ-Amino Esters via Pd-Catalyzed Asymmetric Allylic Amination
  作者：Chao Xia、Jiefeng Shen、Delong Liu、Wanbin Zhang

  DOI：10.1021/acs.orglett.7b01904

  日期：2017.8.18

  A Pd-catalyzed asymmetric allylic amination of 4-substituted 2-acetoxybut-3-enoates with amines has been developed for the regiospecific synthesis of chiral α,β-unsaturated γ-amino esters. The desired chiral aminated products can be obtained in up to 98% yield, and 99% ee and can be conveniently transformed to chiral γ-amino acid/alcohol derivatives and chiral γ-lactams, which can then be subjected

  已经开发了Pd催化的4-取代的2-乙酰氧基丁-3-烯酸酯与胺的不对称烯丙基胺化，用于手性α，β-不饱和γ-氨基酯的区域特异性合成。可以以高达98％的收率和99％ee的产率获得所需的手性胺化产物，并且可以方便地将其转化为手性γ-氨基酸/醇衍生物和手性γ-内酰胺，然后可以对其进行几种类型的合成手性药物和候选药物。手性γ-氨基酯的优先形成可能归因于烯丙基底物右侧的庞大取代基。这项工作为合成手性α，β-不饱和γ-氨基酯及其衍生物提供了有效的策略。