trans-3-diethoxyphosphoryl-1,4-diphenyl-azetidin-2-one | 119288-67-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酰胺类
• 英文名称: trans-3-diethoxyphosphoryl-1,4-diphenyl-azetidin-2-one
• 英文别名: diethyl trans-2-oxo-1,4-diphenylazetidine-3-phosphonate；diethyl (+/-)-trans-1,4-diphenyl-2-oxo-azetidin-3-yl-phosphonate；(3S,4S)-3-diethoxyphosphoryl-1,4-diphenylazetidin-2-one
• CAS: 119288-67-4
• 化学式: C₁₉H₂₂NO₄P
• 分子量: 359.362
• InChiKey: MZLDMLCVLDQLHB-ROUUACIJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  25
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  55.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  苯甲醛 、 trans-3-diethoxyphosphoryl-1,4-diphenyl-azetidin-2-one 在 sodium hydride 作用下， 以80%的产率得到(Z)-3-Benzyliden-1,4-diphenylazetidin-2-one
  参考文献：
  名称：

  (二乙基膦酰基)烯酮的环加成反应

  摘要：

  在某些情况下，发现甲基和氯（二乙基膦酰基）烯酮以不寻常的方式添加到环戊二烯或亚胺中。检查了环加合物的一些化学转化和霍纳-维蒂希反应。

  DOI：

  10.1246/cl.1988.211
• 作为产物：
  描述：

  [(benzyl-phenyl-carbamoyl)-methyl]-phosphonic acid diethyl ester 在 dirhodium tetraacetate 、 对甲苯磺酰叠氮 、 sodium hydride 作用下， 以 四氢呋喃 、 1,2-二氯乙烷 为溶剂， 反应 26.5h， 生成 trans-3-diethoxyphosphoryl-1,4-diphenyl-azetidin-2-one
  参考文献：
  名称：

  Rh(II)-Catalyzed Intramolecular C−H Insertion of Diazo Substrates in Water:  Scope and Limitations

  摘要：

  Preferential Rh(II) carbenoid intramolecular C-H versus O-H insertion derived from R-diazo-acetamides can be achieved in water by using an appropriate combination of the catalyst and amide groups, which creates a larger hydrophobic environment around the reactive carbenoid center.

  DOI：

  10.1021/jo060397a

文献信息

• Stereoselective control in the Staudinger reactions involving monosubstituted ketenes with electron acceptor substituents: experimental investigation and theoretical rationalization
  作者：Hengzhen Qi、Xinyao Li、Jiaxi Xu

  DOI：10.1039/c0ob00783h

  日期：——

  The stereoselectivity of the Staudinger reactions involving monosubstituted ketenes with electron acceptor substituents was investigated experimentally by determination of the product stereochemistry and theoretically via DFT calculations. The results indicate that imines preferentially attack the less sterically hindered exo-side of the ketenes to generate zwitterionic intermediates. Subsequently, for cyclic imines, the intermediates undergo a conrotatory ring closure directly to produce β-lactams, while for linear imines, the imine moiety of the intermediates isomerizes to more stable intermediates, which further undergo a conrotatory ring closure to afford trans-β-lactams. The steric hindrance and the isomerization, rather than the torquoelectronic effect, play crucial roles in controlling the stereoselectivity in the practical Staudinger reactions involving monosubstituted ketenes with electron acceptor substituents, although the unaccessible borylketene with a powerful electron acceptor group controls the stereoselectivity torquoelectronically, in theory.

  通过确定产物立体化学和基于密度泛函理论（DFT）的计算，实验上研究了涉及带有电子受体取代基的单取代乙烯酮的斯陶丁格反应的立体选择性。结果表明，亚胺优先攻击乙烯酮上立体障碍较小的外侧，生成内鎓离子中间体。随后，对于环状亚胺，中间体直接进行协同环合反应生成β-内酰胺；而对于线性亚胺，中间体的亚胺部分异构化为更稳定的中间体，后者进一步进行协同环合反应，产生反式β-内酰胺。在实际涉及带有电子受体取代基的单取代乙烯酮的斯陶丁格反应中，立体障碍和异构化而不是扭曲电子效应在控制立体选择性中起着关键作用，尽管在理论上，具有强电子受体基团的不可获得的硼乙烯酮通过扭曲电子效应控制立体选择性。
• Application of diethyl ethynephosphonate for the synthesis of 3-phosphonylated β-lactams via Kinugasa reaction
  作者：Marcin K. Kowalski、Grzegorz Mlostoń、Emilia Obijalska、Heinz Heimgartner

  DOI：10.3998/ark.5550190.p009.660

  日期：——

  The easily available diethyl ethynylphosphonate reacts with diverse aldonitrones under Kinugasa reaction conditions at room temperature, providing 3-phosphonylated beta-lactams in good yields. In all cases, the reaction led to the trans-isomer exclusively. The trans-configuration was assigned based on 1H-NMR spectroscopic analysis.

  容易获得的乙炔基膦酸二乙酯在室温下在衣笠反应条件下与各种醛硝酮反应，以良好的产率提供 3-膦酰化的 β-内酰胺。在所有情况下，反应仅导致反式异构体。基于 1 H-NMR 光谱分析指定反式构型。
• Rh(<scp>ii</scp>) catalysed intramolecular C–H insertion of diazo substrates in water: a simple and efficient approach to catalyst reuse
  作者：Nuno R. Candeias、Pedro M. P. Gois、Carlos A. M. Afonso

  DOI：10.1039/b414233k

  日期：——

  Water is an efficient solvent for the Rh2(OAc)4 catalysed intramolecular C-H insertion of a range of diazo substrates without competitive water insertion. Due to the high solubility and stability of the catalyst in water, the catalyst can be efficiently reused.

  水是Rh2（OAc）4催化的一系列重氮底物分子内CH插入的有效溶剂，而没有竞争性的水插入。由于催化剂在水中的高溶解度和稳定性，因此可以有效地重复使用催化剂。
• Simple Approach to β-Lactam Derivatives from <i>N</i>-Acylimidazoles
  作者：Moshe Nahmany、Artem Melman

  DOI：10.1021/jo0607010

  日期：2006.7.1

  Reaction of N-acylimidazoles possessing an electron-withdrawing group in the alpha position with diarylimines produces beta-lactams in high yields.