(Z)-dimethyl (2-acetamido-2-phenylvinyl)phosphonate | 1115365-44-0

• 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: (Z)-dimethyl (2-acetamido-2-phenylvinyl)phosphonate
• 英文别名: N-[(Z)-2-[dimethoxy(oxido)phosphaniumyl]-1-phenylethenyl]acetamide
• CAS: 1115365-44-0
• 化学式: C₁₂H₁₆NO₄P
• 分子量: 269.237
• InChiKey: SQJLCUQZTRDOKM-XFXZXTDPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  70.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (Z)-dimethyl (2-acetamido-2-phenylvinyl)phosphonate 在 bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate 、 (R,S)-Josiphos 、 氢气 作用下， 以 甲醇 为溶剂， 20.0~22.0 ℃ 、506.66 kPa 条件下， 反应 30.0h， 以72%的产率得到dimethyl 2-acetylamino-2-phenylethylphosphonate
  参考文献：
  名称：

  Rhodium complexes of (R)-Me-CATPHOS and (R)-(S)-JOSIPHOS: highly enantioselective catalysts for the asymmetric hydrogenation of (E)- and (Z)-β-aryl-β-(enamido)phosphonates

  摘要：

  Rhodium complexes of (R)-Me-CATPHOS and (R)-(S)-JOSIPHOS form a complementary pair of catalysts for the highly efficient asymmetric hydrogenation of a selection of (E)- and (Z)-beta-aryl-beta-(enamido)phosphonates, respectively, in the majority of cases giving excellent yields and ee's in excess of 99%: the highest to be reported for this Class Of substrate. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2009.05.023
• 作为产物：
  描述：

  1-(乙酰氨基)-1-苯乙烯 、 亚磷酸二甲酯 在 manganese(III) acetylacetonate 作用下， 以 甲苯 为溶剂， 反应 24.0h， 以52%的产率得到(Z)-dimethyl (2-acetamido-2-phenylvinyl)phosphonate
  参考文献：
  名称：

  室温下乙酰丙酮锰（III）介导的磷酸化

  摘要：

  在温和条件下，乙酰丙酮锰（III）介导的酰胺和氧化膦的交叉脱氢偶联具有高度的Z选择性磷酸化作用。该反应显示出广泛的底物范围和官能团相容性。DFT研究表明Z产物的形成大概是由于分子内氢键的存在。可以通过还原和水解产物轻松获得β-氨基膦。

  DOI：

  10.1002/adsc.201800585

文献信息

• Pd(II)-Catalyzed Phosphorylation of Enamido C(sp² )-H Bonds: A General Route to β-Amido-vinylphosphonates
  作者：Baokun Qiao、Hao-Qiang Cao、Yin-Jun Huang、Yue Zhang、Jing Nie、Fa-Guang Zhang、Jun-An Ma

  DOI：10.1002/cjoc.201800262

  日期：2018.9

  the synthesis of C–P bonds has been an important focus of research. We herein report a Pd‐catalyzed enamido C(sp2)–H phosphorylation for direct construction of C–P bonds under simple and convenient conditions without the need for additional ligands or directing groups. The present reaction can tolerate a wide range of functional groups, and furnish a variety of phosphorylation products including t

  有机磷化合物是现代制药，农业化学和材料科学中必不可少的结构。新型的合成C-P键的有效方法一直是研究的重点。我们在此报告了一种Pd催化的烯键化C（sp 2）-H磷酸化，可在简单方便的条件下直接构建C-P键，而无需其他配体或指导基团。本反应可耐受多种官能团，并提供多种磷酸化产物，包括四取代乙烯基β-氨基膦酸酯，否则很难获得。该方案还被例示为生物活性天然产物的后期修饰，适用于大规模合成。
• Rh-catalyzed asymmetric hydrogenation of α- and β-enamido phosphonates: highly enantioselective access to amino phosphonic acids
  作者：Hong-Quan Du

  DOI：10.1039/d2ob01419j

  日期：——

  Catalytic asymmetric hydrogenation of α- and β-enamido phosphonates was developed using a complex formed in situ through a chiral hybrid phosphine-bicyclic bridgehead phosphoramidite ligand and rhodium metal precursor as the catalyst. This strategy afforded a wide variety of substrates in excellent yield (96–99%) and enantiomeric excess (≤99%) with very low catalyst loading (S/C up to 10 000) and relatively

  使用通过手性杂化膦-双环桥头亚磷酰胺配体和铑金属前体原位形成的络合物作为催化剂，开发了 α- 和 β- 烯酰氨基膦酸酯的催化不对称氢化。该策略以极低的催化剂负载量（S/C 高达 10 000）和相对温和的反应条件提供了多种底物，具有出色的收率（96-99%）和对映体过量（≤99%）。进一步的研究表明氢化反应只发生在 C没有互变异构化为亚胺形式的烯酰胺磷酸酯阶段的 C 键。氢化产物的串联水解反应以相当高的产率得到相应的 α- 和 β- 氨基膦酸，可作为生物有机化学、药物化学和有机合成的多用途基础材料。
• Rhodium-Catalyzed Enantioselective Hydrogenation of Unsaturated Phosphonates by ClickFerrophos Ligands
  作者：Takashi Konno、Kenta Shimizu、Kenichi Ogata、Shin-ichi Fukuzawa

  DOI：10.1021/jo300129m

  日期：2012.4.6

  Newly developed ClickFerrophos II ligands were applied in the hydrogenation of alpha,beta-unsaturated phosphonates. The use of a rhodium/ClickFerrophos II catalyst was examined in the hydrogenation of fimctionalized alpha,beta-unsaturated phosphonates and was revealed to be effective for beta-alkyl-beta-aryl or beta-dialkyl phosphonates, (Z)-beta-enolester phosphonates, and alpha-phenylethenyl phosphonates, producing the corresponding chiral phosphonates in good yields with high enantioselectivities (up to 96% ee).
• Manganese(III) Acetylacetonate-Mediated Phosphorylation of Enamides at Room Temperature
  作者：Yue Liu、Zhanxiang Liu、Yuhong Zhang、Chunhua Xiong

  DOI：10.1002/adsc.201800585

  日期：2018.9.17

  A highly Z‐selective phosphorylation by Manganese(III) acetylacetonate‐mediated cross‐dehydrogenative‐coupling of enamides and phosphine oxides has been developed under mild conditions. The reaction shows broad substrate scope and functional group compatibility. DFT studies revealed that the formation of Z‐products is presumably due to the presence of an intramolecular hydrogen bond. β‐Aminophosphine

  在温和条件下，乙酰丙酮锰（III）介导的酰胺和氧化膦的交叉脱氢偶联具有高度的Z选择性磷酸化作用。该反应显示出广泛的底物范围和官能团相容性。DFT研究表明Z产物的形成大概是由于分子内氢键的存在。可以通过还原和水解产物轻松获得β-氨基膦。
• Rhodium complexes of (R)-Me-CATPHOS and (R)-(S)-JOSIPHOS: highly enantioselective catalysts for the asymmetric hydrogenation of (E)- and (Z)-β-aryl-β-(enamido)phosphonates
  作者：Simon Doherty、Julian G. Knight、Adam L. Bell、Shireen El-Menabawey、Christopher M. Vogels、Andreas Decken、Stephen A. Westcott

  DOI：10.1016/j.tetasy.2009.05.023

  日期：2009.7

  Rhodium complexes of (R)-Me-CATPHOS and (R)-(S)-JOSIPHOS form a complementary pair of catalysts for the highly efficient asymmetric hydrogenation of a selection of (E)- and (Z)-beta-aryl-beta-(enamido)phosphonates, respectively, in the majority of cases giving excellent yields and ee's in excess of 99%: the highest to be reported for this Class Of substrate. (C) 2009 Elsevier Ltd. All rights reserved.