tert-butyl (2S)-2-[dimethoxyphosphoryl(hydroxy)methyl]pyrrolidine-1-carboxylate | 603956-48-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: tert-butyl (2S)-2-[dimethoxyphosphoryl(hydroxy)methyl]pyrrolidine-1-carboxylate
• CAS: 603956-48-5
• 化学式: C₁₂H₂₄NO₆P
• 分子量: 309.299
• InChiKey: UTDNRJWDPKBWLX-RGURZIINSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  85.3
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  tert-butyl (2S)-2-[dimethoxyphosphoryl(hydroxy)methyl]pyrrolidine-1-carboxylate 在 二乙胺基三氟化硫 、 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 8.33h， 生成 tert-butyl N-[(2S,3S)-1-[(2S)-2-[[dimethoxy(oxido)phosphaniumyl]-fluoromethyl]pyrrolidin-1-yl]-3-methyl-1-oxopentan-2-yl]carbamate
  参考文献：
  名称：

  β-Fluorinated proline derivatives: potential transition state inhibitors for proline selective serine dipeptidases

  摘要：

  Three new types of beta-fluorinated proline derivatives were synthesized as potential transition state inhibitors for proline selective serine dipeptidases. The fluorophosponate derived from protected proline was tested as a Wadsworth-Horner-Emmons reagent for the synthesis of fluoro-olefin-containing pseudodipeptides. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(02)02764-8
• 作为产物：
  描述：

  (S)-N-Boc-吡咯烷-2-甲醛 N-(叔丁氧羰基)-L-脯氨醛 、 亚磷酸二甲酯 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 反应 1.0h， 以93%的产率得到tert-butyl (2S)-2-[dimethoxyphosphoryl(hydroxy)methyl]pyrrolidine-1-carboxylate
  参考文献：
  名称：

  β-Fluorinated proline derivatives: potential transition state inhibitors for proline selective serine dipeptidases

  摘要：

  Three new types of beta-fluorinated proline derivatives were synthesized as potential transition state inhibitors for proline selective serine dipeptidases. The fluorophosponate derived from protected proline was tested as a Wadsworth-Horner-Emmons reagent for the synthesis of fluoro-olefin-containing pseudodipeptides. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(02)02764-8

文献信息

• A novel hydrogen migration of dialkylphosphonic acid esters using electrospray ionization tandem mass spectrometry
  作者：Zhiping Zeng、Ping Luo、Yao Jiang、Yan Liu、Guo Tang、Pengxiang Xu、Yufen Zhao

  DOI：10.1002/rcm.5215

  日期：2011.11.15

  analysis of the fragmentation of α-hydroxy-β-amino phosphonate esters designed as inhibitors of protein kinase A. An interesting proton migration mechanism in the cleavage of the P-C bond is investigated by electrospray ionization tandem mass spectrometry. A possible rearrangement mechanism is proposed and verified by high-resolution mass spectra using isotope deuterium/hydrogen-exchange technology and additionally

  在本文中，注意力集中在分析设计为蛋白激酶A抑制剂的α-羟基-β-氨基膦酸酯的片段化上。通过电喷雾电离串联质谱研究了PC键断裂中有趣的质子迁移机理。提出了一种可能的重排机制，并使用同位素氘/氢交换技术通过高分辨率质谱进行了验证，并通过基于高斯软件的详细DFT计算进行了检查。结果清楚地表明，该机理以化合物3f的活化能为11.3 kcal mol（-1）的五元环协同过渡态进行。整个反应是吸热的，能量为13.2 kcal mol（-1）。通过实验和理论研究了不同取代基和不同金属离子对这些酯重排的影响。结论是，这种重排过程在能量上不利，因此仅在质谱仪中发生。
• β-Fluorinated proline derivatives: potential transition state inhibitors for proline selective serine dipeptidases
  作者：Pieter Van der Veken、Kristel Senten、István Kertèsz、Achiel Haemers、Koen Augustyns

  DOI：10.1016/s0040-4039(02)02764-8

  日期：2003.1

  Three new types of beta-fluorinated proline derivatives were synthesized as potential transition state inhibitors for proline selective serine dipeptidases. The fluorophosponate derived from protected proline was tested as a Wadsworth-Horner-Emmons reagent for the synthesis of fluoro-olefin-containing pseudodipeptides. (C) 2003 Elsevier Science Ltd. All rights reserved.