diethyl (R)-(-)-(1-amino-3-methylbutyl)phosphonate | 159171-46-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: diethyl (R)-(-)-(1-amino-3-methylbutyl)phosphonate
• 英文别名: (R)-diethyl 1-amino-3-methylbutylphosphonate；diethyl (R)-1-amino-3-methylbutylphosphonate；(R)-(1-amino-3-methylbutyl)phosphonic acid diethyl ester；(R)-1-Amino-3-methylbutylphosphonic acid diethyl ester；(1R)-1-diethoxyphosphoryl-3-methylbutan-1-amine
• CAS: 159171-46-7
• 化学式: C₉H₂₂NO₃P
• 分子量: 223.252
• InChiKey: TVBLDWTXOYRRKF-SECBINFHSA-N

物化性质

• 沸点：
  288.8±23.0 °C(Predicted)
• 密度：
  1.022±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  14
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  61.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  diethyl (R)-(-)-(1-amino-3-methylbutyl)phosphonate 在 盐酸 作用下， 反应 16.0h， 以83%的产率得到(R)-1-磷酰-3-甲基丁胺
  参考文献：
  名称：

  Enantioselective Synthesis of Diverse .alpha.-Amino Phosphonate Diesters

  摘要：

  An efficient, versatile protocol for the synthesis of highly enantioenriched alpha-amino phosphonate diesters has been devised. Addition of lithium diethyl phosphite to chiral chelating imines 31a-j, prepared from a variety of aldehydes and the chiral auxiliary (R)-(-)-1-amino-1-phenyl-2-methoxyethane (29), generated predominantly the (R,R) diastereomers 33. Hydrogenolysis then furnished alpha-amino phosphonates 15; in most examples, the enantiomeric purity exceeded 97% ee.

  DOI：

  10.1021/ja00149a011
• 作为产物：
  描述：

  ((R)-2-Methoxy-1-phenyl-ethyl)-[3-methyl-but-(E)-ylidene]-amine 在 palladium dihydroxide 氢气 作用下， 以 四氢呋喃 为溶剂， 反应 20.0h， 生成 diethyl (R)-(-)-(1-amino-3-methylbutyl)phosphonate
  参考文献：
  名称：

  Asymmetric Synthesis of .alpha.-Aminophosphonates via Diastereoselective Addition of Lithium Diethyl Phosphite to Chelating Imines

  摘要：

  DOI：

  10.1021/ja00099a084

文献信息

• The Assignment of the Absolute Configuration of Diethyl Hydroxy- and Aminophosphonates by ¹H and ³¹P NMR Using Naproxen as a Reliable Chiral Derivatizing Agent
  作者：Katarzyna Błażewska、Piotr Paneth、Tadeusz Gajda

  DOI：10.1021/jo062097z

  日期：2007.2.1

  The assignment of the absolute configuration of hydroxy- and aminophosphonates by their double derivatization with commercially available naproxen is presented. The correlation between the spatial arrangement around the stereogenic carbon center and the signs of the ΔδRS allows determination of the absolute configuration of hydroxy- and aminophosphonates by simple comparison of the 1H and 31P NMR spectra

  提出了羟基膦酸酯和氨基膦酸酯的绝对构型通过与市售萘普生的双衍生作用的分配。周围的立构碳中心的空间排列和Δδ的符号之间的相关性RS通过简单比较（R）-和（S）-萘普生酯或酰胺衍生物的1 H和31 P NMR光谱，可以确定羟基和氨基膦酸酯的绝对构型。NMR研究对结构多样的萘普生酯和羟基膦酸酯和氨基膦酸酯的酰胺进行了广泛的构象分析（理论计算，低温实验），证明了可以成功使用简化的模型。
• A New Enzyme Model For Enantioselective Esterases Based On Molecularly Imprinted Polymers
  作者：Marco Emgenbroich、Günter Wulff

  DOI：10.1002/chem.200304783

  日期：2003.9.5

  site monomer 1. After polymerization and removal of the template, the polymers were efficient catalysts for the hydrolysis of certain nonactivated amino acid phenylesters (2 L, 2 D, 3 L, 3 D) depending on the template used. Imprinted catalyst IP4 (imprinted with 4 L) enhanced the hydrolysis of the corresponding substrate 2 L by a factor of 325 relative to that of a buffered solution. Relative to a control

  通过使用分子印迹技术制备了显示对映选择性酯酶活性的有效酶模型。合成对映体纯的膦酸单酯4 L和5 L作为稳定的过渡态类似物。它们用作通过化学计量非共价相互作用连接到两当量的idi键结合位点单体1的模板。聚合并除去模板后，这些聚合物是某些非活化氨基酸苯基酯（2 L，2 D， 3 L，3 D），具体取决于所使用的模板。压印的催化剂IP4（压印有4 L）使相应的底物2 L的水解度比缓冲溶液的水解度提高了325倍。相对于不含模板4 L的含相同官能团的对照聚合物，增强效果仍然约为80倍，显示了迄今为止最高的压印效果。在交叉选择性实验中，尽管底物和模板的结构存在细微差异，但仍发现大于3的强底物选择性。水解的初始速度与底物浓度的关系图显示了具有饱和行为的典型Michaelis-Menten动力学。从这些曲线，可以计算出米氏常数K（M）和催化常数k（cat）。这些值中显示的对映选择性是最令人感兴趣的。用IP4水解2
• Employing a chiroptical sensor for the absolute stereochemical determination of α-amino and α-hydroxyphosphonates
  作者：Debarshi Chakraborty、Li Zheng、Yijing Dai、Jeff Gwasdacus、James E. McTighe、William D. Wulff、Babak Borhan

  DOI：10.1039/d3cc01757e

  日期：——

  The absolute stereochemistry of the α-amino and α-hydroxyphosphonates is determined using a chiroptical sensor. The induced helicity of the host–guest complex is correlated to the chirality of the guest molecule via a simple binding model. The relative size of the substituents dictates the predominant helical population, leading to an easy circular dichroic readout.

  使用手性光学传感器测定α-氨基和α-羟基膦酸酯的绝对立体化学。主客体复合物的诱导螺旋性通过简单的结合模型与客体分子的手性相关。取代基的相对大小决定了主要的螺旋群，从而实现简单的圆二色性读数。
• ASYMMETRIC SYNTHESIS OF DIETHYL (R)-(−)-(1-AMINO-3-METHYLBUTYL)PHOSPHONATE
  作者：Smith, Amos B.、Yager, Kraig M.、Phillips, Barton W.、Taylor, Carol M.

  DOI：10.15227/orgsyn.075.0019

  日期：——
• Enantioselective synthesis of diethyl 1-hydroxyalkylphosphonates via oxazaborolidine catalyzed borane reduction of diethyl α-ketophosphonates
  作者：Tadeusz Gajda

  DOI：10.1016/s0957-4166(00)86271-0

  日期：1994.10

  Reduction of diethyl alpha-ketophosphonates 1 with borane and B-butyloxazaborolidine 2 as catalyst afforded diethyl (S)- or (R)-1-hydroxyalkylphosphonates 3a-d or 3e-f respectively in good yields and moderate to good enantiomeric excess (53-83 ee%). Respective diethyl (R)- and (S)-1-aminoalkylphosphonates 6 were obtained in a one-pot transformation, by the Mitsunobu reaction of 1-hydroxyphosphonates 3 with hydrazoic acid, and subsequent treatment of the intermediate azides 4, with triphenylphosphine, followed by hydrolysis df the iminophosphoranes 5 with water.