(2R)-3-diphenylphosphinothioyl-2-(9H-fluoren-9-ylmethoxycarbonylamino)propanoic acid | 157825-94-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: (2R)-3-diphenylphosphinothioyl-2-(9H-fluoren-9-ylmethoxycarbonylamino)propanoic acid
• CAS: 157825-94-0
• 化学式: C₃₀H₂₆NO₄PS
• 分子量: 527.581
• InChiKey: PVSOQQQXDYNWMD-NDEPHWFRSA-N

物化性质

• 密度：
  1.36±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.7
• 重原子数：
  37
• 可旋转键数：
  9
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  108
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (2R)-3-diphenylphosphinothioyl-2-(9H-fluoren-9-ylmethoxycarbonylamino)propanoic acid 在 1-羟基苯并三唑 、 溶剂黄146 、 1-(3-二甲基氨基丙基)-3-乙基碳二亚胺 、 锌 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 25.5h， 生成 (S)-2-[(R)-3-(Diphenyl-phosphinothioyl)-2-(9H-fluoren-9-ylmethoxycarbonylamino)-propionylamino]-propionic acid
  参考文献：
  名称：

  Structure of Phosphorus-Containing Peptide Ligands. X-ray and NMR Structural Study of Free Ligand and Rhodium Complex

  摘要：

  The structure of a series of phosphorus-containing peptides was studied, The X-ray structure of a phosphorus-containing dodecapeptide is reported. Analysis of the solution structure of similar phosphorus-containing peptides before and after coordination of rhodium is also reported. In both the solid state and in solution, the peptides were found to exist in a mixture of a-helical and 3(10) helical conformations. Coordination of rhodium to the i, i + 4 orientated phosphine groups appears to alter the conformational preference.

  DOI：

  10.1021/jo970773e
• 作为产物：
  描述：

  methyl (R)-2-amino-3-(diphenylphosphorothioyl)propanoate hydrochloride 在 水 、 碳酸氢钠 、 lithium hydroxide 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 水 为溶剂， 反应 6.0h， 生成 (2R)-3-diphenylphosphinothioyl-2-(9H-fluoren-9-ylmethoxycarbonylamino)propanoic acid
  参考文献：
  名称：

  基于天然产物Gramicidin S的双膦功能化环十肽：过渡金属配位的潜在支架

  摘要：

  天然产物Gramicidin S是新型寡肽双膦配体的有前途的支架，将有利的刚性手性骨架与膦取代基紧密结合在一起。通过一种涉及手性镍席夫碱模板的对映选择性烷基化的新方案，合成了所需的非天然的，含膦的氨基酸构件。制备了三个Ni配合物，其中膦基和掺入的甘氨酸的α-碳原子之间具有不同的烷基链；其中两个的绝对立体化学是通过单晶X射线结构分析确定的。通过分离模板，对映体L膦氨基酸使固相，逐步构建膦修饰的寡肽的线性序列成为可能。在环化过程中，产生了三个双膦取代的Gramicidin S类似物，只是膦基和寡肽骨架之间的连接大小和形状不同。它们的晶体结构表明这些物质具有作为螯合配体的潜力。

  DOI：

  10.1002/chem.200901127

文献信息

• High Asymmetric Induction with β-Turn-Derived Palladium Phosphine Complexes
  作者：Scott J. Greenfield、Anton Agarkov、Scott R. Gilbertson

  DOI：10.1021/ol035097j

  日期：2003.8.1

  [reaction: see text] Work toward the development of a bisphosphine ligand system for the palladium-catalyzed addition to cyclic allyl acetates is reported. A parallel approach using phosphine-containing amino acids in conjunction with natural amino acids was used to develop a selective ligand system. The ligand system was examined while attached to the polymer support as well as in solution. Selectivites

  [反应：见正文]据报道，人们正在努力开发双膦配体体系，用于钯催化环乙酸烯丙酯的加成反应。使用含膦氨基酸和天然氨基酸的平行方法开发了选择性配体系统。在连接到聚合物载体以及溶液中的同时检查配体体系。据报道，具有困难的底物3-乙酰氧基环戊烯的ee高达95％ee。
• Catalysis with Phosphine-Containing Amino Acids in Various “Turn” Motifs
  作者：Anton Agarkov、Scott J. Greenfield、Takahiro Ohishi、Scott E. Collibee、Scott R. Gilbertson

  DOI：10.1021/jo049103g

  日期：2004.11.1

  We have been actively involved in the development of parallel approaches for the discovery of phosphine ligands. Our approach has been based on the incorporation of phosphine-containing amino acids into peptide sequences that are designed to have stable secondary structures. We have examined helical and turn secondary structures and have reported that alkylation of cyclopentenyl acetate with dimethylmalonate can be catalyzed in high enantiomeric excess (ee) with a beta-turn-based ligand. The importance of the peptide secondary structure was demonstrated through the synthesis of a series of peptide ligands where the nature of the turn-forming residues was probed. Additionally, other turn-forming units and a variety of different phosphine-containing amino acids have been examined for their ability to control the selectivity of the allylation reaction. This paper reports the results obtained through the examination of different turn motifs as well as different phosphine substitutions on the "best" turn sequence, Pps-Pro-D-Xxx-Pps.
• Gilbertson; Chen Guohua; McLoughlin, Journal of the American Chemical Society, 1994, vol. 116, # 10, p. 4481 - 4482
  作者：Gilbertson、Chen Guohua、McLoughlin

  DOI：——

  日期：——
• Bisphosphine-Functionalized Cyclic Decapeptides Based on the Natural Product Gramicidin S: A Potential Scaffold for Transition-Metal Coordination
  作者：Sebastian Burck、Sander G. A. van Assema、Bas Lastdrager、J. Chris Slootweg、Andreas W. Ehlers、José M. Otero、Bruno Dacunha-Marinho、Antonio L. Llamas-Saiz、Mark Overhand、Mark J. van Raaij、Koop Lammertsma

  DOI：10.1002/chem.200901127

  日期：2009.8.17

  The natural product Gramicidin S is a promising scaffold for novel oligopeptide‐based bisphosphine ligands, combining the advantageous rigid chiral backbone with the close proximity of phosphine substituents. The required unnatural, phosphine‐containing, amino acid building blocks were synthesized by means of a novel protocol that involves the enantioselective alkylation of a chiral nickel Schiff base

  天然产物Gramicidin S是新型寡肽双膦配体的有前途的支架，将有利的刚性手性骨架与膦取代基紧密结合在一起。通过一种涉及手性镍席夫碱模板的对映选择性烷基化的新方案，合成了所需的非天然的，含膦的氨基酸构件。制备了三个Ni配合物，其中膦基和掺入的甘氨酸的α-碳原子之间具有不同的烷基链；其中两个的绝对立体化学是通过单晶X射线结构分析确定的。通过分离模板，对映体L膦氨基酸使固相，逐步构建膦修饰的寡肽的线性序列成为可能。在环化过程中，产生了三个双膦取代的Gramicidin S类似物，只是膦基和寡肽骨架之间的连接大小和形状不同。它们的晶体结构表明这些物质具有作为螯合配体的潜力。
• Structure of Phosphorus-Containing Peptide Ligands. X-ray and NMR Structural Study of Free Ligand and Rhodium Complex
  作者：Scott R. Gilbertson、Guohua Chen、Jeff Kao、Alicia Beatty、Charles F. Campana

  DOI：10.1021/jo970773e

  日期：1997.8.1

  The structure of a series of phosphorus-containing peptides was studied, The X-ray structure of a phosphorus-containing dodecapeptide is reported. Analysis of the solution structure of similar phosphorus-containing peptides before and after coordination of rhodium is also reported. In both the solid state and in solution, the peptides were found to exist in a mixture of a-helical and 3(10) helical conformations. Coordination of rhodium to the i, i + 4 orientated phosphine groups appears to alter the conformational preference.