dimethyl (R)-hydroxy(4-nitrophenyl)methylphosphonate

• 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: dimethyl (R)-hydroxy(4-nitrophenyl)methylphosphonate
• 英文别名: dimethyl (R)-hydroxy(p-nitrophenyl)methylphosphonate；dimethyl [hydroxy(4-nitrophenyl)methyl]phosphonate；(R)-dimethoxyphosphoryl-(4-nitrophenyl)methanol
• 化学式: C₉H₁₂NO₆P
• 分子量: 261.171
• InChiKey: WKULVHLZPACKQK-SECBINFHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  102
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  dimethyl (4-nitrobenzyl)phosphonate 在 (+)-(8,8-dichlorocamphorylsulfonyl)-oxaziridine 、 sodium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 生成 (S)-dimethyl hydroxy(4-nitrophenyl)methylphosphonate 、 dimethyl (R)-hydroxy(4-nitrophenyl)methylphosphonate
  参考文献：
  名称：

  Enantioselective synthesis of α-hydroxy phosphonates via oxidation with (camphorsulfonyl)oxaziridines

  摘要：

  Reaction of phosphonate anions with enantiomerically pure (camphorsulfonyl)oxaziridines results in formation of nonracemic alpha-hydroxy phosphonates. This enantioselective hydroxylation methodology provides convenient access to optically active alpha-hydroxy phosphonates and their corresponding phosphonic acids. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(97)00705-3

文献信息

• Synthesis of an Optically Active Al(salalen) Complex and Its Application to Catalytic Hydrophosphonylation of Aldehydes and Aldimines
  作者：Bunnai Saito、Hiromichi Egami、Tsutomu Katsuki

  DOI：10.1021/ja0651005

  日期：2007.2.1

  serve as an efficient catalyst for hydrophosphonylation of aldehydes and aldimines, giving the corresponding alpha-hydroxy and alpha-amino phosphonates with high enantioselectivity, respectively. The scope of the hydrophosphonylation was wide, and both aliphatic and aromatic aldehydes and aldimines were successfully used as substrates for the reaction. The potent catalysis of the complex is attributed to

  以模块化合成方式新合成了光学活性铝（salalen）配合物2，发现它可作为醛和醛亚胺氢膦酰化的有效催化剂，分别得到相应的具有高对映选择性的α-羟基和α-氨基膦酸酯. 氢膦酰化的范围很广，脂肪族和芳香族醛和醛亚胺都成功地用作反应的底物。该复合物的强大催化作用归因于其独特的结构：它采用扭曲的三角双锥体构型，这使得 salalen 配体呈顺式-β 样结构，其中手性氨基位于靠近金属中心的位置。
• Organocatalytic enantioselective hydrophosphonylation of aldehydes
  作者：Juan V. Alegre-Requena、Eugenia Marqués-López、Pablo J. Sanz Miguel、Raquel P. Herrera

  DOI：10.1039/c3ob42403k

  日期：——

  our results concerning the first squaramide-catalysed hydrophosphonylation of aldehydes. In all cases, the reactions proceeded smoothly and cleanly under mild reaction conditions rendering final α-hydroxy phosphonates in very good yields and high enantioselectivities. It is one of the few organocatalytic examples of this reaction using aldehydes. It is the first time that diphenylphosphite (1e) has

  我们报告有关醛的第一个方胺催化的氢膦酰化反应的结果。在所有情况下，反应均在温和的反应条件下平稳而干净地进行，从而以非常好的收率和高对映选择性产生最终的α-羟基膦酸酯。它是使用醛的该反应的少数有机催化实例之一。与先前公开的方法中使用的亚磷酸二烷基酯相反，这是首次将亚磷酸二苯基酯（1e）成功用于醛的手性Pudovik反应中，从而扩大了这种不对称方法的通用性。
• Catalytic Asymmetric Synthesis of α-Hydroxy Phosphonates Using the Al−Li−BINOL Complex
  作者：Takayoshi Arai、Masahiro Bougauchi、Hiroaki Sasai、Masakatsu Shibasaki

  DOI：10.1021/jo960180o

  日期：1996.1.1
• Synthesis of Nonracemic Dimethyl α-(Hydroxyfarnesyl)phosphonates via Oxidation of Dimethyl Farnesylphosphonate with (Camphorsulfonyl)oxaziridines
  作者：Diana M. Cermak、Yanming Du、David F. Wiemer

  DOI：10.1021/jo980984z

  日期：1999.1.1

  Several strategies for synthesis of nonracemic dimethyl alpha-(hydroxyfarnesyl)phosphonate and the parent phosphonic acid have been explored. Separation of diastereomeric derivatives prepared by esterification of racemic a-hydroxy phosphonate with (S)-(+)-O-methylmandelic acid was possible, and these diastereomers could be assigned absolute stereochemistry on the basis of literature precedent; However, hydrolysis to the alpha-hydroxy phosphonic acid was accompanied by extensive isomerization. Addition of a nonracemic phosphonamidite to farnesal also gave nonracemic material, but again hydrolysis was problematic. Oxidation of dimethyl farnesylphosphonate anion with nonracemic (camphorsulfonyl)oxaziridines was shown to be regio- and stereoselective for formation of the a-hydroxy phosphonate. Enantiomeric excess of similar to 70% ee was established by conversion of the oxidation products to their (S)-(+)-O-methylmandelate derivatives. Although hydrolysis of these methyl esters was accompanied by extensive racemization, both enantiomers of alpha-(hydroxyfarnesyl)phosphonic acid were obtained in low ee by this strategy.
• Synthesis of an Optically ActiveC1-Symmetric Al(salalen) Complex and Its Application to the Catalytic Hydrophosphonylation of Aldehydes
  作者：Bunnai Saito、Tsutomu Katsuki

  DOI：10.1002/anie.200501008

  日期：2005.7.18