tert-butyl 2-oxo-4-phenylbut-3-ynoate | 883581-66-6

• 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: tert-butyl 2-oxo-4-phenylbut-3-ynoate
• 英文别名: tert-butyl 2-oxo-4-phenyl-3-butynoate
• CAS: 883581-66-6
• 化学式: C₁₄H₁₄O₃
• 分子量: 230.263
• InChiKey: BWUUZGVYKZGLRY-UHFFFAOYSA-N

物化性质

• 沸点：
  323.0±25.0 °C(Predicted)
• 密度：
  1.12±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  tert-butyl 2-oxo-4-phenylbut-3-ynoate 在 三乙烯二胺 、 (S)-3,3'-bis(2,4,6-tri-iso-propylphenyl)-1,1'-binaphthyl-2,2'-diyl hydrogenphosphate 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 24.0h， 生成 2-benzyl 3-(tert-butyl) (R)-5-phenyl-3-(1H-pyrrol-2-yl)isoxazole-2,3(3H)-dicarboxylate
  参考文献：
  名称：

  杂芳烃与原位生成的异恶唑鎓离子通过手性磷酸催化的对映选择性 Aza-Friedel-Crafts 反应

  摘要：

  开发了一种不对称的有机催化氮杂-弗里德尔-克拉夫茨反应，以从良好到优异的产率和对映选择性（50-99%，55-> 99% ee）得到带有季取代立体中心的对映体富集的 Δ 4 -异恶唑啉支架。该协议涉及在手性磷酸存在下原位生成的异恶唑离子，然后通过不对称反阴离子导向催化进行杂芳烃加成。

  DOI：

  10.1002/adsc.202100408
• 作为产物：
  描述：

  tert-butyl glyoxylate 在 manganese(IV) oxide 、 甲基溴化镁 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 为溶剂， 反应 2.0h， 生成 tert-butyl 2-oxo-4-phenylbut-3-ynoate
  参考文献：
  名称：

  Inactivation of the phenylpyruvate tautomerase activity of macrophage migration inhibitory factor by 2-oxo-4-phenyl-3-butynoate

  摘要：

  Macrophage migration inhibitory factor (MIF) is an important immunoregulatory protein that has been implicated in several inflammatory diseases. MIF also has a phenylpyruvate tautomerase (PPT) activity, the role of which remains elusive in these biological activities. The acetylene compound, 2-oxo-4-phenyl-3-butynoate (2-OPB), has been synthesized and tested as a potential irreversible inhibitor of its enzymatic activity. Incubation of the compound with MIF results in the rapid and irreversible loss of the PPT activity. Mass spectral analysis established that the amino-terminal proline, previously implicated as a catalytic base in the PPT-catalyzed reaction, is the site of covalent modification. Inactivation of the PPT activity likely occurs by a Michael addition of Pro-1 to C-4 of the inhibitor. Attempts to crystallize the inactivated complex to confirm the structure of the adduct on the covalently modified Pro-1 by X-ray crystallography were not successful. Nor was it possible to unambiguously interpret electron density observed in the active sites of the native crystals soaked with the inhibitor. This may be due to crystal packing in that the side chain of Glu-16 from an adjacent trimer occupies one active site. However, this crystal contact may be partially responsible for the high-resolution quality of these MIF crystals. Nonetheless, because MIF is a member of the tautomerase superfamily, a group of structurally homologous proteins that share a beta-alpha-beta structural motif and a catalytic Pro-1, 2-OPB may find general use as a probe of tautomerase superfamily members that function as PPTs.

  DOI：

  10.1016/j.bioorg.2006.05.001

文献信息

• An Unprecedented Organocascade Synthesis of Functionalized Bicyclic Nitrones from 2‐Aminomalonate Derived Nucleophiles and 1‐Nitro‐1,3‐Enynes via Allenes Formation and Subsequent Rearrangement
  作者：Wan‐Yun Huang、Ramani Gurubrahamam、Kwunmin Chen

  DOI：10.1002/adsc.201801161

  日期：2019.1.11

  An efficient organocatalytic cascade reaction for synthesising functionalized bicyclic nitrones is reported. The reaction of dielectrophilic ethyl 2‐(nitromethylene)‐4‐arylbut‐3‐ynoate and (E)‐diethyl 2‐((2‐hydroxybenzylidene)‐amino)malonates to give a unique nitrone scaffold in the presence of a catalytic amount of DABCO is described. The working mechanism was proposed to proceed with allene formation

  报道了用于合成官能化的双环硝酮的有效的有机催化级联反应。在介电量的催化下，2-（硝基亚甲基）-4-芳基丁3-壬酸酯和（E）二乙基2-（（2-羟基苄叉基）-氨基）丙二酸酯的反应生成了独特的硝酮骨架。描述了DABCO。提出了工作机理，以进行亚丙基形成，然后进行分子内环化和硝基中氧原子的重排。在这种简便的化学转化过程中，获得了广泛的底物，其中以优异的非对映选择性（> 20：1 dr）以中等至良好的收率（19％至79％）分离出双环硝酮。
• Three-Component Assembly and Divergent Ring-Expansion Cascades of Functionalized 2-Iminooxetanes
  作者：Weijun Yao、Lianjie Pan、Yiping Zhang、Gang Wang、Xiaoqin Wang、Cheng Ma

  DOI：10.1002/anie.201004685

  日期：2010.11.22

  A bold diversification strategy: Aromatic alkynes, p‐toluenesulfonyl azide, and aromatic 2‐oxobut‐3‐ynoates underwent a copper(I)‐catalyzed multicomponent reaction to provide functionalized 2‐iminooxetanes 1, which could be converted selectively into five‐membered nitrogen‐containing heterocycles of two different sorts, depending on the reaction conditions (see scheme; Tf=trifluoromethanesulfonyl;

  大胆的多元化战略：芳烃，对甲苯磺酰叠氮化物和芳族2-氧代丁3酸酯进行铜（I）催化的多组分反应，以提供功能化的2-亚氨基氧杂环丁烷1，可以选择性地将其转化为五元氮取决于反应条件（参见方案； Tf =三氟甲磺酰基； R = Et，i Pr）包含两种不同类型的杂环。
• Organocatalytic Nitroaldol Reaction Associated with Deuterium-Labeling
  作者：Tsuyoshi Yamada、Marina Kuwata、Ryoya Takakura、Yasunari Monguchi、Hironao Sajiki、Yoshinari Sawama

  DOI：10.1002/adsc.201701224

  日期：2018.2.15

  A deuterium‐labeling reaction of nitroalkanes in deuterium oxide and the subsequent nitroaldol reaction have been accomplished under basic and organocatalytic conditions to provide the deuterium‐labeled β‐nitroalcohols in high yields and high deuterium contents. β‐Deuterated β‐nitroalcohols could be smoothly obtained from the reaction of nitroalkanes and various electrophiles using the easily‐removal

  在碱性和有机催化条件下，已经完成了氧化氘中的硝基链烷烃的氘标记反应和随后的硝基醛反应，从而以高收率和高氘含量提供了氘标记的β-硝基醇。使用易去除的碱性树脂WA30，可通过硝基烷与各种亲电试剂的反应平稳地获得β氘代的β硝基醇。此外，在奎宁衍生的有机催化剂存在下，使用硝基甲烷和α-酮酸酯作为亲电试剂的不对称硝基醛醇反应可提供所需的具有高对映选择性的β-氘代硝基醇衍生物。
• One-pot, cis-selective synthesis of α-substituted β-trimethylsilyl-α,β-epoxyesters from α-ketoesters and diazo(trimethylsilyl)methyl magnesium bromide
  作者：Yoshiyuki Hari、Susumu Tsuchida、Toyohiko Aoyama

  DOI：10.1016/j.tetlet.2006.01.067

  日期：2006.3

  Reaction of α-ketoesters with diazo(trimethylsilyl)methyl magnesium bromide followed by in situ treatment with pivalic acid gave α-substituted β-trimethylsilyl-α,β-epoxyesters in an efficient and cis-selective manner.

  α-酮酸酯与重氮（三甲基甲硅烷基）甲基溴化镁反应，然后用新戊酸原位处理，可以高效，顺式选择性地得到α-取代的β-三甲基甲硅烷基-α，β-环氧酯。
• Asymmetric Catalytic Synthesis of Epoxides via Three-Component Reaction of Diazoacetates, 2-Oxo-3-ynoates, and Nitrosoarenes
  作者：Yu Zhang、Hao Pan、Wen Liu、Weidi Cao、Xiaoming Feng

  DOI：10.1021/acs.orglett.0c02108

  日期：2020.9.4

  An enantioselective three-component reaction of diazoacetates, 2-oxo-3-ynoates, and nitrosoarenes has been developed by using a chiral N,N′-dioxide/Ni(OTf)2 complex. This catalytic manifold allows rapid access to a series of multifunctional chiral epoxides containing an imino ketone substituent in moderate to good yields (up to 82%) and excellent diastereo- and enantioselectivities (up to >95/5 dr

  通过使用手性N，N'-二氧化物/ Ni（OTf）2络合物，已开发出重氮乙酸酯，2-氧代-3-炔酸酯和亚硝基芳烃的对映选择性三组分反应。该催化歧管允许以中等到良好的收率（高达82％）以及出色的非对映和对映选择性（高达> 95/5 dr和99％ee）快速访问一系列含有亚氨基酮取代基的多功能手性环氧化物。在温和的反应条件下，Z / E比的水平（高达> 95/5 Z / E）。