2-[(Z)-1-diethoxyphosphoryl-4-methylpent-1-en-2-yl]isoindole-1,3-dione | 1449520-37-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异吲哚及其衍生物
• 英文名称: 2-[(Z)-1-diethoxyphosphoryl-4-methylpent-1-en-2-yl]isoindole-1,3-dione
• CAS: 1449520-37-9
• 化学式: C₁₈H₂₄NO₅P
• 分子量: 365.366
• InChiKey: PGMPCGOSMHAAIQ-OWBHPGMISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  25
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  72.9
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  (S)-diethyl (1-diazo-2-(1,3-dioxoisoindolin-2-yl)-4-methylpentyl)phosphonate 在 silver trifluoromethanesulfonate 、 四(3,5-二(三氟甲基)苯基)硼酸钠 作用下， 以 甲基叔丁基醚 为溶剂， 反应 7.5h， 以60%的产率得到
  参考文献：
  名称：

  区域专一和β-氨基（高度立体选择性合成Ž）-enylphosphonates经由通过的AgOTf催化二烷基α-diazophosphonates的β氢迁移反应†

  摘要：

  为了研究金属卡宾在1,2-迁移反应中的空间效应，已经从天然氨基酸制备了一系列带有不同取代基的二烷基α-重氮膦酸酯。使用AgOTf / NaBAr F络合物对重氮膦酸酯进行重氮分解，导致β氢迁移，从而以高收率和高区域选择性和立体选择性得到β-氨基（Z）-烯基膦酸酯。一种可能的反应机理表明，空间效应会极大地影响几何异构性。这种构造（Z）-β-氨基乙烯基膦酸酯的新方法应该在有机合成中具有普遍的用途。

  DOI：

  10.1039/c4ra02520b

文献信息

• Regiospecific and highly stereoselective synthesis of β-amino (Z)-enylphosphonates via β-hydrogen migration reaction of dialkyl α-diazophosphonates catalyzed by AgOTf
  作者：Yan Cai、Haihong Ge、Chengbin Yu、Weize Sun、Junchen Zhan、Zhiwei Miao

  DOI：10.1039/c4ra02520b

  日期：——

  to give β-amino (Z)-enylphosphonates in good yields with high regio- and stereoselectivity. A possible reaction mechanism shows that the steric effect could dramatically influence the geometric isomerism aptitude. This new method for constructing (Z)-β-amino vinylphosphonates should be of general utility in organic synthesis.

  为了研究金属卡宾在1,2-迁移反应中的空间效应，已经从天然氨基酸制备了一系列带有不同取代基的二烷基α-重氮膦酸酯。使用AgOTf / NaBAr F络合物对重氮膦酸酯进行重氮分解，导致β氢迁移，从而以高收率和高区域选择性和立体选择性得到β-氨基（Z）-烯基膦酸酯。一种可能的反应机理表明，空间效应会极大地影响几何异构性。这种构造（Z）-β-氨基乙烯基膦酸酯的新方法应该在有机合成中具有普遍的用途。
• Unexpected Stereoselective Synthesis of (<i>Z</i>)-β-Alkenyl Substituted β-Amino Phosphonates through β,γ-Dihydrogen Shift Reaction Catalyzed by a Copper(I) Complex and Iodine [Cu(MeCN)₄]PF₆/I₂
  作者：Yan Cai、Hairong Lyu、Chengbin Yu、Zhiwei Miao

  DOI：10.1002/adsc.201300838

  日期：2014.2.10

  AbstractA series of dialkyl α‐diazophosphonates has been prepared from natural amino acids. The diazo decomposition of these diazophosphonate compounds with tetrakis(acetonitrile)copper(I) hexafluorophosphate/iodine, [Cu(MeCN)4]PF6/I2, as catalyst has been investigated. It was found that the diazo decomposition of dialkyl α‐diazophosphonates gave a mixture of β,γ‐dihydrogen shift and 1,2‐hydride migration products and afforded β‐alkenyl‐substituted β‐amino phosphonates with the Z configuration. The mechanism of this novel diazo decomposition process was discussed.magnified image
• 1,2-Hydride Migration in Dialkyl α-Diazophosphonates Catalyzed by [Cu(MeCN)4]PF6: A Novel Approach to β-Amino (E)-Enylphosphonates
  作者：Zhiwei Miao、Haihong Ge、Shuang Liu、Yan Cai、Yuchao Sun

  DOI：10.1055/s-0035-1560373

  日期：——

  The regiospecific and stereoselective 1,2-migration reaction of dialkyl alpha-diazophosphonates for the synthesis of beta-amino (E)-enylphosphonates is developed utilizing tetrakis(acetonitrile)copper(I) hexafluorophosphate [Cu(MeCN)(4)PF6] as the catalyst and N,N-dimethylformamide as an additive. A possible mechanism for the 1,2-migration reaction involving a metal carbene is presented. An investigation on the E/Z isomer selectivity of this process demonstrates that steric factors play an important role on the outcome. This process provides a straightforward access to beta-amino (E)-enylphosphonates in moderate to good yields.