3-(E)-2-pentenoyl-1,3-oxazolidin-2-one | 192379-68-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: 3-(E)-2-pentenoyl-1,3-oxazolidin-2-one
• 英文别名: 3-(trans-2'-pentenoyl)oxazolidin-2-one；3-[(E)-2-pentenoyl]-2-oxazolidinone；3-((2E)-pentenoyl)-2-oxazolidinone；3-[(E)-pent-2-enoyl]-1,3-oxazolidin-2-one
• CAS: 192379-68-3
• 化学式: C₈H₁₁NO₃
• 分子量: 169.18
• InChiKey: AGZDHBMAFHMZLO-ONEGZZNKSA-N

物化性质

• 沸点：
  234.7±23.0 °C(Predicted)
• 密度：
  1.193±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-(E)-2-pentenoyl-1,3-oxazolidin-2-one 在 N,N-二异丙基乙胺 sodium tetrahydroborate 、 4 A molecular sieve 、 水 、 magnesium triflimide 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 9.0h， 生成 (4S,5R)-1-(4-bromophenyl)-4,5-dihydro-4-ethyl-5-hydroxymethyl-3-phenyl-1H-pyrazole
  参考文献：
  名称：

  An Entry to a Chiral Dihydropyrazole Scaffold:  Enantioselective [3 + 2] Cycloaddition of Nitrile Imines

  摘要：

  We have developed a versatile strategy to access dihydropyrazoles in highly enantioenriched form. Dipolar cycloaddition of electron-deficient acceptors and in situ-generated nitrile imines proceeds with high regio- and enantioselectivity using 10 mol % chiral Lewis acid catalyst. A variety of dihydropyrazoles that incorporate functionality for further manipulation have been prepared.

  DOI：

  10.1021/ja051650b
• 作为产物：
  描述：

  2-唑烷酮 、 (E)-pent-2-enoyl chloride 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 0.75h， 以22%的产率得到3-(E)-2-pentenoyl-1,3-oxazolidin-2-one
  参考文献：
  名称：

  Dendritic Bis(oxazoline)copper(II) Catalysts. 2.¹ Synthesis, Reactivity, and Substrate Selectivity

  摘要：

  A series of dendritic bis(oxazoline) Ligands 1-4 were synthesized to evaluate the effects of the degree of branching of a dendritic sector on both the reactivity and selectivity of their corresponding copper(II) complex-catalyzed Diels-Alder reaction between cyclopentadiene and a crotonyl imide. Kinetic studies unveiled a two-step mechanism of the Diels-Alder reaction, in which a reversible binding of the dienophile to the copper complex was followed by a rate-determining reaction between the resulting dienophile-catalyst complex with the diene. Furthermore, two interesting features emerged: first, the formation constant of the dienophile-catalyst complex decreased gradually on going from the lower to higher generations, and secondly, while the Diels-Alder reaction rate constant remained essentially the same from the zeroth to second generation catalysts, it dropped abruptly for the third generation one. These observations were rationalized as a consequence of a folding-back of the dendritic sectors toward the catalytic unit at the third generation, so that increase in steric size impeded both the reactivity and binding profiles of the catalytic system. This behavior was reminiscent of related phenomena observed by others from solvatomatic, photophysical, and viscosity studies. In line with this reasoning, a slight but noticeable substrate selectivity was observed for the third generation catalyst, which was absence for the lower ones, in competitive kinetic studies involving two dienophiles of different steric sizes.

  DOI：

  10.1021/jo970383s

文献信息

• Synthetic Study of Diversifolin:  The Construction of 11-Oxabicyclo[6.2.1]undec-3-ene Core Using Ring-Closing Metathesis
  作者：Tomoaki Nakamura、Motoko Oshida、Tomoko Nomura、Atsuo Nakazaki、Susumu Kobayashi

  DOI：10.1021/ol7025119

  日期：2007.12.1

  Stereoselective synthesis of a potential intermediate bearing 11-oxabicyclo[6.2.1]undec-3-ene core, a common scaffold of biologically active germacrane-type sesquiterpenes, has been achieved. Synthetic features involve formal 1,3-asymmetric induction, unusual ring-closing metathesis constructing a 10-membered carbocycle system, and unique lactone transposition.

  已经实现了立体选择性合成的潜在中间体，该中间体带有11-氧杂双环[6.2.1]十一碳-3-烯核，这是一种具有生物活性的ac草型倍半萜的常见骨架。合成特征涉及正式的1,3-不对称诱导，构建10元碳环系统的不寻常的闭环复分解反应以及独特的内酯转座。
• <i>C</i>₂-Symmetric Bissulfoximines as Ligands in Copper-Catalyzed Enantioselective Diels−Alder Reactions
  作者：Carsten Bolm、Marc Martin、Oliver Simic、Marinella Verrucci

  DOI：10.1021/ol027273e

  日期：2003.2.1

  [reaction: see text] Bissulfoximines have been used as chiral ligands in copper-catalyzed enantioselective Diels-Alder reactions between acryloyl-2-oxazolidinones and cyclopentadiene. After optimizing the ligand structure, the metal source, the counterions, and the solvent, products with up to 93% ee have been obtained.

  [反应：见正文]在铜催化的丙烯酰基-2-恶唑烷酮与环戊二烯之间的对映选择性Diels-Alder反应中，双硫肟酮已被用作手性配体。在优化配体结构，金属源，抗衡离子和溶剂后，可得到ee高达93％的产品。
• Catalytic Enantioselective Conjugate Addition of Nitromethane to α′-Hydroxy Enones as Surrogates of α,β-Unsaturated Carboxylic Acids and Aldehydes
  作者：Claudio Palomo、Raquel Pazos、Mikel Oiarbide、Jesús M. García

  DOI：10.1002/adsc.200606076

  日期：2006.7

  No base is required for the Mg(II)-catalyzed conjugate addition of nitromethane to α′-hydroxy enones in the presence of molecular sieves. Good enantioselectivities are attained using 3 or 4 Å MS and about 10 mol % of Mg(OTf)2-chiral bisoxazoline complexes. Elaboration of the adducts through oxidative cleavage of the ketol moiety provides an entry to enantioenriched γ-nitro carboxylic acids, while a

  在分子筛存在下，Mg（II）催化的硝基甲烷与α'-羟基烯酮的共轭加成反应不需要碱。使用3或4ÅMS和约10 mol％的Mg（OTf）2-手性双恶唑啉配合物可获得良好的对映选择性。通过酮醇部分的氧化裂解来精制加合物，可提供对映体富集的γ-硝基羧酸，而依次进行的羰基还原-二醇氧化可产生相应的醛。
• Michael Addition Reactions between Chiral Ni(II) Complex of Glycine and 3-(<i>trans</i>-Enoyl)oxazolidin-2-ones. A Case of Electron Donor−Acceptor Attractive Interaction-Controlled Face Diastereoselectivity¹
  作者：Chaozhong Cai、Vadim A. Soloshonok、Victor J. Hruby

  DOI：10.1021/jo0014865

  日期：2001.2.1

  noyl)oxazolidin-2-ones was found to depend exclusively on the steric bulk of the alkyl group on the starting Michael acceptor. In contrast, the face diastereoselectivity in the reactions of aromatic oxazolidin-2-ones with the Ni(II) complex of glycine was shown to be controlled predominantly by the electronic properties of the aryl ring. In particular, the additions of the Ni(II) complex of glycine

  这项研究表明，具有高亲电性和构象均一性的，容易获得且便宜的3-（反式3'-烷基/芳基丙烯酰基）恶唑烷-2-酮是合成的迈克尔受体，优于常规使用的烷基烯醇酸酯，因此与甘氨酸的手性席夫碱的Ni（II）配合物与（S）-o- [N-（N-（苄基脯氨酰基）氨基]二苯甲酮的加成反应的反应活性和大多数情况下的非对映选择性显着提高。系统地研究了甘氨酸的Ni（II）配合物和恶唑烷-2-酮之间相应的迈克尔加成反应中的动力学控制的非对映选择性，它是取代基对起始迈克尔受体的空间，电子和位置效应的函数。在脂族和芳族系列中，发现简单的非对映选择性实际上都是完整的，从而通过相应的TS生成了具有类似进场几何形状的产物。发现甘氨酸的Ni（II）配合物与3-（反式3'-烷基丙烯酰基）恶唑烷丁-2-酮之间的反应的表面非对映选择性仅取决于起始迈克尔受体上烷基的空间体积。相反，芳族恶唑烷-2-酮与甘氨酸的Ni（II）配合物的反应中的
• Asymmetric Conjugate Addition of <i>O</i>-Benzylhydroxylamine to α,β-Unsaturated 3-Acyloxazolidin-2-ones Catalyzed by Sc(OTf)₃/<i>i</i>-Pr-Pybox Complex
  作者：Shin-ichi Fukuzawa、Satoshi Kikuchi、Hiroaki Sato

  DOI：10.1055/s-2006-939068

  日期：——

  The asymmetric conjugate addition of O-benzylhydroxylamine to α,β-unsaturated 3-acyloxazolidin-2-ones was smoothly catalyzed by the Sc(OTf)3/2,6-bis[(S)-4-isopropyloxazolin-2-yl]pyridine (i-Pr-pybox) complex in the presence of MS 4 Å to give the corresponding β-amino acids in good conversions with high enan­tioselectivities (up to 91% ee).

  O-苄基羟胺与 α,β-不饱和 3-acyloxazolidin-2-ones 的不对称共轭加成由 Sc(OTf)3/2,6-bis[(S)-4-isopropyloxazolin-2-yl 顺利催化] 吡啶 (i-Pr-pybox) 复合物在 MS 4 Å 存在下以良好的转化率得到相应的β-氨基酸，具有高对映选择性（高达 91% ee）。