(S)-diethyl (1-diazo-2-(1,3-dioxoisoindolin-2-yl)propyl)phosphonate | 1449519-80-5

• 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: (S)-diethyl (1-diazo-2-(1,3-dioxoisoindolin-2-yl)propyl)phosphonate
• 英文别名: 2-[(2S)-1-diazo-1-diethoxyphosphorylpropan-2-yl]isoindole-1,3-dione
• CAS: 1449519-80-5
• 化学式: C₁₅H₁₈N₃O₅P
• 分子量: 351.299
• InChiKey: UKOFPRYDRFHVCV-JTQLQIEISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  24
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  74.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (S)-diethyl (1-diazo-2-(1,3-dioxoisoindolin-2-yl)propyl)phosphonate 在 tetrakis(actonitrile)copper(I) hexafluorophosphate 、 N,N-二甲基甲酰胺 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以53%的产率得到(E)-diethyl [2-(1,3-dioxoisoindolin-2-yl)prop-1-en-1-yl]phosphonate
  参考文献：
  名称：

  1,2-Hydride Migration in Dialkyl α-Diazophosphonates Catalyzed by [Cu(MeCN)4]PF6: A Novel Approach to β-Amino (E)-Enylphosphonates

  摘要：

  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.

  DOI：

  10.1055/s-0035-1560373
• 作为产物：
  描述：

  (S)-2-phthalimidopropionyl chloride 在 盐酸 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 30.0h， 生成 (S)-diethyl (1-diazo-2-(1,3-dioxoisoindolin-2-yl)propyl)phosphonate
  参考文献：
  名称：

  Combined C–H functionalization/O–H insertion reaction to form tertiary β-alkoxy substituted β-aminophosphonates catalyzed by [Cu(MeCN)4]PF6

  摘要：

  已开发出以碘为添加剂的铜催化的α-二氮基膦酸酯与醇的C–H功能化/O–H插入反应。为了解释这一反应，我们在此提出了一个可能的联合作用机制。该过程可直接获得具有中到良好产率的叔β-醇氧基取代的β-氨基膦酸酯衍生物。

  DOI：

  10.1039/c3ob40941d

文献信息

• Trifluoroborane-Catalyzed C–H Functionalization/S–H Insertion Reaction: Construction of N,S-Acetal Quaternary Centers
  作者：Yan Cai、Haihong Ge、Weize Sun、Zhiwei Miao

  DOI：10.1055/s-0034-1380384

  日期：2015.6

  The trifluoroborane-catalyzed C–H functionalization/S–H insertion reaction of α-diazophosphonates with thiols has been developed. A plausible reaction mechanism has been proposed to understand the combined reaction. This process provides straightforward access to N,S-acetals containing quaternary centers in moderate to good yields and chemoselectivity.

  三氟硼烷催化的α-重氮磷酸酯与硫醇的C-H官能化/S-H插入反应已经被开发出来。已经提出了一个合理的反应机理来理解这个复合反应。这个过程以中等到良好的产率和化学选择性提供了直接访问含有季铵中心的N,S-缩醛。
• Regioselective BF₃·Et₂O-catalyzed C–H functionalization of indoles and pyrrole with reaction of α-diazophosphonates
  作者：Yan Cai、Yuming Li、Minxuan Zhang、Jiaxin Fu、Zhiwei Miao

  DOI：10.1039/c6ra15329a

  日期：——

  insertion reactions of α-diazophosphonates with indole or pyrrole derivatives catalyzed by trifluoroborane have been developed. The reaction protocol was effective for regioselective C–H insertion depending on the substitution pattern on the indole moiety and carbene migratory model. This represents the first straightforward access to N-unsubstituted β-(3-indol)-β-aminophosphonates and β-(2-pyrrol)-β-aminophosphonates

  已经开发出α-重氮膦酸酯与三氟硼烷催化的吲哚或吡咯衍生物的区域特异性分子间C–H插入反应。根据吲哚部分的取代方式和卡宾迁移模型，该反应方案对于区域选择性C–H插入是有效的。这代表了以中等到良好的产率首次直接获得含有季碳中心的N-未取代的β-（3-吲哚）-β-氨基膦酸酯和β-（2-吡咯）-β-氨基膦酸酯。
• 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
• Combined C–H functionalization/O–H insertion reaction to form tertiary β-alkoxy substituted β-aminophosphonates catalyzed by [Cu(MeCN)4]PF6
  作者：Yan Cai、Yuchen Lu、Chengbin Yu、Hairong Lyu、Zhiwei Miao

  DOI：10.1039/c3ob40941d

  日期：——

  The copper-catalyzed C–H functionalization/O–H insertion reaction of α-diazophosphonates with alcohols has been developed with iodine as an additive. In order to understand this reaction, we present here a possible mechanism for the combined reaction. This process provides straightforward access to tertiary β-alkoxy substituted β-aminophosphonate derivatives with moderate to good yields.

  已开发出以碘为添加剂的铜催化的α-二氮基膦酸酯与醇的C–H功能化/O–H插入反应。为了解释这一反应，我们在此提出了一个可能的联合作用机制。该过程可直接获得具有中到良好产率的叔β-醇氧基取代的β-氨基膦酸酯衍生物。