tetra-o-nitrobenzylpyrophosphate | 1401995-67-2

• 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: tetra-o-nitrobenzylpyrophosphate
• 英文别名: 1-[[[Bis[(2-nitrophenyl)methoxy]-oxidophosphaniumyl]oxy-[(2-nitrophenyl)methoxy]-oxidophosphaniumyl]oxymethyl]-2-nitrobenzene
• CAS: 1401995-67-2
• 化学式: C₂₈H₂₄N₄O₁₅P₂
• 分子量: 718.464
• InChiKey: SDGIBKQOSYERDP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  49
• 可旋转键数：
  14
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  276
• 氢给体数：
  0
• 氢受体数：
  15

反应信息

• 作为反应物：
  描述：

  2-十二烷醇 、 tetra-o-nitrobenzylpyrophosphate 在 titanium(IV) tetrabutoxide 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 18.0h， 以92%的产率得到2-dodecyl di-o-nitrobenzyl phosphate
  参考文献：
  名称：

  Catalytic Lewis acid phosphorylation with pyrophosphates

  摘要：

  We report a method for the Lewis acid catalyzed phosphorylation of alcohols with pyrophosphates. Ti((OBu)-Bu-t)(4) was found to be the most effective catalyst in the phosphorylation of both primary and secondary alcohols with tetrabenzylpyrophosphate, providing conversions between 54% and >98% and isolated yields between 50% and 97%. Other pyrophosphates with orthogonal protecting groups were synthesized and screened to validate the generality of the approach. This study will describe how benzyl, methyl, ethyl, allyl, and o-nitrobenzyl pyrophosphates are all effective phosphorylating agents under Lewis acid catalysis. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2012.08.070
• 作为产物：
  描述：

  di-o-nitrobenzyl pyrophosphate 在 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 以88%的产率得到tetra-o-nitrobenzylpyrophosphate
  参考文献：
  名称：

  Catalytic Lewis acid phosphorylation with pyrophosphates

  摘要：

  We report a method for the Lewis acid catalyzed phosphorylation of alcohols with pyrophosphates. Ti((OBu)-Bu-t)(4) was found to be the most effective catalyst in the phosphorylation of both primary and secondary alcohols with tetrabenzylpyrophosphate, providing conversions between 54% and >98% and isolated yields between 50% and 97%. Other pyrophosphates with orthogonal protecting groups were synthesized and screened to validate the generality of the approach. This study will describe how benzyl, methyl, ethyl, allyl, and o-nitrobenzyl pyrophosphates are all effective phosphorylating agents under Lewis acid catalysis. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2012.08.070

文献信息

• Desymmetrization of Diols by Phosphorylation with a Titanium-BINOLate Catalyst
  作者：Erik T. Ouellette、Marshall G. Lougee、Andrea R. Bucknam、Paul J. Endres、John Y. Kim、Emma J. Lynch、Elizabeth J. Sisko、Bianca R. Sculimbrene

  DOI：10.1021/acs.joc.1c00414

  日期：2021.6.4

  incorporating a protected amine. The chiral ligand, base, solvent, and stoichiometry are evaluated along with a nonlinear effect study to support an active catalyst species that is oligomeric in chiral ligand. The use of pyrophosphates as the phosphorylating agent in the desymmetrization facilitates a user-friendly method for enantioselective phosphorylation with desirable protecting groups (benzyl, o-nitrobenzyl)

  讨论了通过磷酰基转移与钛-BINOLate 络合物对十个前手性二醇的去对称化。九个 1,3-丙二醇的磷酸化以 50-98% 的产率实现。对映体比率高达 92:8 的二醇可实现含有季 C-2 中心并结合受保护胺的二醇。手性配体、碱、溶剂和化学计量与非线性效应研究一起进行评估，以支持手性配体中的低聚活性催化剂种类。在去对称化中使用焦磷酸盐作为磷酸化剂促进了一种用户友好的方法，用于在磷酸盐产物上使用所需的保护基团（苄基，邻硝基苄基）进行对映选择性磷酸化。