dimethyl (Z)-2-acetylamino-2-p-tolylvinylphosphonate | 1115365-48-4

• 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: dimethyl (Z)-2-acetylamino-2-p-tolylvinylphosphonate
• 英文别名: (Z)-dimethyl 2-acetamido-2-p-tolylvinylphosphonate；N-[(Z)-2-[dimethoxy(oxido)phosphaniumyl]-1-(4-methylphenyl)ethenyl]acetamide
• CAS: 1115365-48-4
• 化学式: C₁₃H₁₈NO₄P
• 分子量: 283.264
• InChiKey: QYRQZXHXAXERCN-LCYFTJDESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 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：

  dimethyl (Z)-2-acetylamino-2-p-tolylvinylphosphonate 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77%的产率得到dimethyl 2-acetylamino-2-p-tolylethylphosphonate
  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：

  dimethyl 2-amino-2-p-tolylvinylphosphonate 、 乙酰氯 在 吡啶 作用下， 以 二氯甲烷 为溶剂， 以54%的产率得到dimethyl (E)-2-acetylamino-2-p-tolylvinylphosphonate
  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

文献信息

• Asymmetric Hydrogenation of α- and β-Enamido Phosphonates: Rhodium(I)/Monodentate Phosphoramidite Catalyst
  作者：Jinzhu Zhang、Yang Li、Zheng Wang、Kuiling Ding

  DOI：10.1002/anie.201104912

  日期：2011.12.2

  High efficiency and enantioselectivity have been achieved in the RhI‐catalyzed asymmetric hydrogenation of α‐ and β‐enamido phosphonates using a monophosphoramidite as the chiral ligand (see scheme; cod=1,5‐cyclooctadiene), thus affording the optically active amino phosphonates with a turnover frequency of up to 1800 h−1 and high ee values.

  使用单亚磷酰胺作为手性配体，在Rh I催化的α-和β-氨基膦酸酯的不对称氢化中实现了高效率和对映选择性（参见方案； cod = 1,5-环辛二烯），从而提供了光学活性的氨基膦酸酯具有高达1800 h -1的周转频率和高ee 值。