4,5-dimethylene-3-(4-methylphenyl)-1,3-oxazolidin-2-one

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4,5-dimethylene-3-(4-methylphenyl)-1,3-oxazolidin-2-one
• 英文别名: 4,5-dimethylene-3-(4-tolyl)oxazolidin-2-one；4,5-Dimethylidene-3-(4-methylphenyl)-1,3-oxazolidin-2-one
• 化学式: C₁₂H₁₁NO₂
• 分子量: 201.225
• InChiKey: RYAKMHHOGPMETL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4,5-dimethylene-3-(4-methylphenyl)-1,3-oxazolidin-2-one 在 sodium tetrahydroborate 、 5% Pd(II)/C(eggshell) 、 三氟化硼乙醚 、 palladium diacetate 、 potassium carbonate 、 溶剂黄146 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 potassium hydroxide 作用下， 以 甲醇 、 乙醇 、 二氯甲烷 、 水 、 丙酮 、 甲苯 为溶剂， 反应 78.42h， 生成 mukoline
  参考文献：
  名称：

  Total Synthesis of the Natural Carbazoles Glycozolicine, Mukoline, and Mukolidine, Starting from 4,5-Dimethyleneoxazolidin-2-ones

  摘要：

  通过应用 4,5-二亚甲基恶唑烷-2-酮与丙烯醛的区域选择性 Diels-Alder 反应，开发了一种新型高效合成天然 1-甲氧基咔唑的方法。环加合物转化为相应的官能化二芳基胺。后者在关键的钯催化下发生环化/脱甲酰化级联反应，从而以较高的总收率制得乙二唑啉。C6 甲基的氧化反应产生了 6-甲酰基咔唑 mukolidine，再将其还原成相应的天然醇 mukoline。

  DOI：

  10.1055/s-0030-1258444
• 作为产物：
  描述：

  对甲苯异氰酸酯 、 2,3-丁二酮 在 lithium carbonate 、 三乙胺 作用下， 以 甲苯 为溶剂， 反应 25.5h， 以65%的产率得到4,5-dimethylene-3-(4-methylphenyl)-1,3-oxazolidin-2-one
  参考文献：
  名称：

  Total Synthesis of the Natural Carbazoles Glycozolicine, Mukoline, and Mukolidine, Starting from 4,5-Dimethyleneoxazolidin-2-ones

  摘要：

  通过应用 4,5-二亚甲基恶唑烷-2-酮与丙烯醛的区域选择性 Diels-Alder 反应，开发了一种新型高效合成天然 1-甲氧基咔唑的方法。环加合物转化为相应的官能化二芳基胺。后者在关键的钯催化下发生环化/脱甲酰化级联反应，从而以较高的总收率制得乙二唑啉。C6 甲基的氧化反应产生了 6-甲酰基咔唑 mukolidine，再将其还原成相应的天然醇 mukoline。

  DOI：

  10.1055/s-0030-1258444

文献信息

• Synthesis and Reactivity of η⁴-Diene-Fe(CO)₃ Complexes from <i>exo</i>-2-Oxazolidinone Dienes. A Facile Generation of Stable Conjugated Enol-Enamido Species
  作者：Fernando Ortega-Jiménez、Adriana Benavides、Francisco Delgado、Hugo A. Jiménez-Vázquez、Joaquín Tamariz

  DOI：10.1021/om900772z

  日期：2010.1.11

  A synthesis of new η4-diene-Fe(CO)3 complexes derived from the novel exo-2-oxazolidinone dienes is described. These complexes were prepared by thermal complexation of the substituted dienes with diiron nonacarbonyl to afford the corresponding complexes as crystal solids. The X-ray single-crystal structure analysis revealed characteristic structural properties for diene-iron complexes, showing that

  新η的合成4 -二烯的Fe（CO）3个配合物从小说衍生外描述了-2-恶唑烷酮二烯。这些配合物是通过将取代的二烯与二铁九碳二烯进行热络合制备的，以提供相应的配合物，为结晶固体。X射线单晶结构分析揭示了二烯-铁配合物的特征结构性质，表明在扭曲的三角锥锥体几何构象中，两个羰基从金属指向金属的顶点C4和C5原子。杂环。通过烯丙基位置的酰化或烷基化对二烯部分的不成功的官能化表明这些二烯的强稳定性。这种稳定性促进了稳定和空前的共轭烯胺-烯醇酯-和en烯-烯醇-Fe（CO）3的生成 通过动力学或热力学控制反应条件形成配合物。
• Hernandez, Raul; Sanchez, Jose M.; Gomez, Adriana, Heterocycles, 1993, vol. 36, # 9, p. 1951 - 1956
  作者：Hernandez, Raul、Sanchez, Jose M.、Gomez, Adriana、Trujillo, Gonzalo、Aboytes, Rossana、et al.

  DOI：——

  日期：——
• One-Step Synthesis and Highly Regio- and Stereoselective Diels−Alder Cycloadditions of Novel <i>exo</i>-2-Oxazolidinone Dienes
  作者：Ashis B. Mandal、Adriana Gómez、Gonzalo Trujillo、Francisco Méndez、Hugo A. Jiménez、María de Jesús Rosales、Rafael Martínez、Francisco Delgado、Joaquín Tamariz

  DOI：10.1021/jo962403g

  日期：1997.6.13

  An improved synthesis of exo-heterocyclic dienes like N-substituted 4,5-dimethylene 2-oxazolidinones 1, by a one-step method from diacetyl and isocyanates, was described. This highly convergent synthetic strategy has been successfully used for the preparation of novel (Z)-5-ethylidene-4-methylene analogs 4 in fair yields. Both dienes 1 and 4 undergo efficient addition of symmetric dienophiles in thermal Diels-Alder reactions, inasmuch as they react stereo- and regioselectively with the unsymmetric olefins methyl vinyl ketone (MVK) and methyl propiolate. This regioselectivity was greatly improved by using Lewis acid catalysts (TiCl4, AlCl3). The nitrogen atom of the 2-oxazolidinone ring seems to control the orientation of the dienophile approach. These results have been rationalized in terms of the frontier molecular orbital theory by ab initio calculations. For dienes 4, addition of MVK gave the endo isomer as the major product. Dimerization of dienes 4 was also highly regio-, chemo-, and stereoselective, giving only isomer 17. This reaction furnished a second product, which corresponded to dienes 18 obtained by the [1,5] sigmatropic rearrangement of 4. The structure of the dienes and main products was established by NMR experiments and X-ray diffraction analysis.
• Synthesis and Cycloaddition Reactions of New Captodative Olefins, N-Substituted 5-Alkylidene-1,3-oxazolidine-2,4-diones
  作者：Joaquín Tamariz、Adriana Benavides、Rafael Martínez、Hugo A. Jiménez-Vázquez、Francisco Delgado、Joaquin Tamariz

  DOI：10.3987/com-00-9094

  日期：——
• Total Synthesis of the Natural Carbazoles Glycozolicine, Mukoline, and Mukolidine, Starting from 4,5-Dimethyleneoxazolidin-2-ones
  作者：Joaquín Tamariz、Rafael Bautista、Pablo Bernal、Luisa Montiel、Francisco Delgado

  DOI：10.1055/s-0030-1258444

  日期：2011.3

  A novel and efficient synthesis of naturally occurring 1-methoxycarbazoles glycozolicine, mukolidine, and mukoline is developed by applying a regioselective Diels-Alder reaction of a 4,5-dimethyleneoxazolidin-2-one with acrolein. The cycloadduct is transformed to the corresponding functionalized diarylamine. The key palladium-catalyzed cyclization/deformylation cascade reaction of the latter leads to glycozolicine in high overall yield. Oxidation of the C6 methyl group provides the 6-formylcarbazole mukolidine, which is reduced to the respective natural alcohol mukoline.

  通过应用 4,5-二亚甲基恶唑烷-2-酮与丙烯醛的区域选择性 Diels-Alder 反应，开发了一种新型高效合成天然 1-甲氧基咔唑的方法。环加合物转化为相应的官能化二芳基胺。后者在关键的钯催化下发生环化/脱甲酰化级联反应，从而以较高的总收率制得乙二唑啉。C6 甲基的氧化反应产生了 6-甲酰基咔唑 mukolidine，再将其还原成相应的天然醇 mukoline。