N-benzyl-N-(tert-butyl)-α-diazo-α-(diethoxyphosphoryl)acetamide | 612096-52-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: N-benzyl-N-(tert-butyl)-α-diazo-α-(diethoxyphosphoryl)acetamide
• 英文别名: diethyl (2-(benzyl(tert-butyl)amino)-1-diazo-2-oxoethyl)phosphonate；N-benzyl-N-tert-butyl-2-diazo-2-diethoxyphosphorylacetamide
• CAS: 612096-52-3
• 化学式: C₁₇H₂₆N₃O₄P
• 分子量: 367.385
• InChiKey: UIKIDOXBMPCQKL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  25
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  57.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  N-benzyl-N-(tert-butyl)-α-diazo-α-(diethoxyphosphoryl)acetamide 在 dirhodium tetraacetate 3-butyl-1-methyl-1H-imidazol-3-ium hexafluorophosphate 作用下， 反应 10.0h， 以76%的产率得到trans-1-(tert-butyl)-3-(diethoxyphosphoryl)-4-phenyl-β-lactam
  参考文献：
  名称：

  Dirhodium(II)-catalysed CH insertion on α-diazo-α-phosphono-acetamides in an ionic liquid

  摘要：

  alpha-Phosphono-lactams were obtained, with high regio and stereo selectivities via Rh-2(OAC)(4)-catalysed intramolecular C-H insertion in an ionic liquid. This system proved to be highly efficient over 5-6 cycles. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(03)01700-3
• 作为产物：
  描述：

  N-benzyl-α-bromoacetyl-N-(tert-butyl)amide 在 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 6.5h， 生成 N-benzyl-N-(tert-butyl)-α-diazo-α-(diethoxyphosphoryl)acetamide
  参考文献：
  名称：

  α-重氮-α-(二烷氧基磷酰基)乙酰胺和-乙酸盐的区域选择性和立体选择性二铑(II)-催化的分子内C-H插入反应

  摘要：

  α-重氮-α-（二烷氧基磷酰基）乙酸酯和 -乙酰胺分别通过二铑（II）催化的分子内碳氢插入反应以中等至高产率提供了 α-（二烷氧基磷酰基）内酯和内酰胺。在α-重氮-α-（二烷氧基磷酰基）乙酰胺的情况下，观察到显着偏好形成γ-内酰胺，立体控制有利于反式非对映异构体。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

  DOI：

  10.1002/ejoc.200300330

文献信息

• Asymmetric Intramolecular CH Insertion of α-Diazoacetamides in Water by Dirhodium(II) Catalysts Derived from Natural Amino Acids
  作者：Nuno R. Candeias、Carolina Carias、Luis F. R. Gomes、Vânia André、M. Teresa Duarte、Pedro M. P. Gois、Carlos A. M. Afonso

  DOI：10.1002/adsc.201200101

  日期：2012.11.12

  The asymmetric dirhodium(II)-catalyzed intramolecular CH insertion of α-diazo acetamides in water is described for the first time. The use of natural α-amino acids as chiral ligands allowed the preparation of novel dirhodium(II) homochiral complexes by a simple procedure consisting of the in situ ligand exchange starting from dirhodium tetraacetate. The catalytic system was further reused up to 7 cycles

  首次描述了α-重氮乙酰胺在水中不对称由二碘鎓（II）催化的分子内CH插入。天然α-氨基酸作为手性配体的使用允许通过简单的程序制备新的dirhodium（II）同手性络合物，该程序包括从四乙酸dirhodium开始的原位配体交换。催化体系进一步重复使用多达7个循环，并以良好的收率和过量的对映异构体获得了β-内酰胺。
• Cyclization of Diazoacetamides Catalyzed by N-Heterocyclic Carbene Dirhodium(II) Complexes
  作者：Carlos Afonso、Luis Gomes、Alexandre Trindade、Nuno Candeias、Luís Veiros、Pedro Gois

  DOI：10.1055/s-0029-1217005

  日期：2009.10

  The axial coordination of N-heterocyclic carbene ligands onto dirhodium(II) complexes was examined, together with its role in the intramolecular C-H insertion reactions of α-diazoacetamides. The formation of a decarbonylated product occurs by a free-carbene mechanism in which the structures of the catalyst and the acetamide play a decisive role. carbenoids - carbene complexes - catalysis - diazo compounds

  研究了N-杂环卡宾配体在dirhodium（II）配合物上的轴向配位，及其在α-重氮乙酰胺的分子内CH插入反应中的作用。脱羰基产物的形成是通过游离碳烯机理进行的，其中催化剂和乙酰胺的结构起决定性作用。 类胡萝卜素-卡宾配合物-催化-重氮化合物-铑
• Intramolecular C–H insertion using NHC–di-rhodium(II) complexes: the influence of axial coordination
  作者：Luis F.R. Gomes、Alexandre F. Trindade、Nuno R. Candeias、Pedro M.P. Gois、Carlos A.M. Afonso

  DOI：10.1016/j.tetlet.2008.10.054

  日期：2008.12

  insertion of diazo-acetamides catalysed by di-rhodium(II) complexes can be highly influenced by the axial ligand on the di-rhodium(II) complex. Axially monocoordinated NHC–Rh2(OAc)4 complexes have a distinct reactivity from the parent Rh2(OAc)4 complex affording the cyclisation products in different rates and selectivities. Surprisingly, a new reaction mode emerged when using these complexes which led

  在这项工作中，我们表明，二铑（II）配合物催化的重氮-乙酰胺分子内CH插入可以受到二铑（II）配合物上的轴向配体的高度影响。轴向单配位NHC-Rh 2（OAc）4复合物与母体Rh 2（OAc）4复合物具有明显的反应性，从而以不同的速率和选择性提供环化产物。出人意料的是，当使用这些络合物时，出现了一种新的反应模式，从而导致了脱羰途径。
• C−H Carbene Insertion of α-Diazo Acetamides by Photolysis in Non-Conventional Media
  作者：Nuno R. Candeias、Pedro M. P. Gois、Luis F. Veiros、Carlos A. M. Afonso

  DOI：10.1021/jo800980c

  日期：2008.8.1

  Light from a mercury vapor high-pressure lamp was used to induce the photolytic decomposition of alpha-diazo acetamides in hexane and in nonconventional media such as water or a film. The corresponding beta- and/or gamma-lactams were obtained in reasonable yields and in some cases with good diastereoselectivities with no need to use a metallic catalyst. Experimental studies on chiral substrates demonstrated the occurrence of insertion with retention of configuration.
• Rh(II)-Catalyzed Intramolecular C−H Insertion of Diazo Substrates in Water:  Scope and Limitations
  作者：Nuno R. Candeias、Pedro M. P. Gois、Carlos A. M. Afonso

  DOI：10.1021/jo060397a

  日期：2006.7.1

  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.